CN106368059B - A kind of preparation method of corrugated paper Cypres and products thereof and application - Google Patents
A kind of preparation method of corrugated paper Cypres and products thereof and application Download PDFInfo
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- CN106368059B CN106368059B CN201610747571.0A CN201610747571A CN106368059B CN 106368059 B CN106368059 B CN 106368059B CN 201610747571 A CN201610747571 A CN 201610747571A CN 106368059 B CN106368059 B CN 106368059B
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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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
-
- 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
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- 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
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic compounds
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/72—Coated paper characterised by the paper substrate
- D21H19/74—Coated paper characterised by the paper substrate the substrate having an uneven surface, e.g. crêped or corrugated paper
-
- 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
- D21H21/16—Sizing or water-repelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention provides a kind of preparation method of corrugated paper Cypres and products thereof and application.Wherein, the corrugated paper Cypres are well mixed obtained by corrugated paper Cypres base-material, cationic additive；The preparation process of corrugated paper Cypres base-material includes：By cationic monomer, siloxanes,（Methyl）Acrylic ester monomer,（Methyl）Styrene, initiator, acetic acid and water are added into reaction vessel, carry out Raolical polymerizable, generate corrugated paper Cypres base-material；The preparation process of cationic additive includes：Alkyl ketene dimer is added into the aqueous solution of cationic emulsifier, is sufficiently stirred, carries out emulsion dispersion, obtains cationic additive.Rapid aging is not only able to according to Cypres made from method provided by the present invention, increases substantially the ring crush intensity of corrugated paper, Cobb values are greatly reduced, and there is very strong anti-performance of getting damp.
Description
Technical field
The invention belongs to papermaking chemical product production field, and in particular to a kind of preparation method of corrugated paper Cypres
With the application as the product obtained by the preparation method, and the product.
Background technology
Corrugated paper is to process the plate object being bonded and the corrugated paper of the waveform formed by sheet lining and by corrugated roller,
Single wall corrugated board and the class of double-layer corrugated cardboard two are generally divided into, is divided into according to the size of corrugation：A, the type of B, C, E, F five.Corrugation
The invention and application of paper have more than 100 years history history, have low cost, light weight, processing is easy, intensity is big, printing adaptability sample is excellent
It is good, storage convenient in carrying the advantages that, more than 80% corrugated paper can be by reclaiming, and corrugated paper can be used as food or number
The packaging of code product, relatively environment-friendly, use is relatively broad.
At present, corrugated board has been obtained as various commodity make packaging and comprehensively popularize, promotion and application.By
In using packing container made of corrugated board to beautifying and protecting built-in commodity to have its unique performance and advantage, its with it is more
Great success is obtained in the competition of kind of packaging material, turns into long so far with not waning and be presented the making bag of fast development
One of main material of packaging container.
Corrugated board generally by facial tissue, inner paper, core paper and is processed into the corrugated paper of waveform corrugation by being bonded.According to
The demand of commodity packaging, corrugated board can be processed into single face corrugated board, triple wall board, five layers, seven layers, eleventh floor etc.
Corrugated board.Wherein, single face corrugated board be typically used as the stickers lining protective layer of commodity packaging or make light card lattice, backing plate with
Vibrations or collision of the commodity in the transportation of storage are protected, three layers most normal in corrugated case is made with five-layers corrugated fiberboard
With.
The packaging of many commodity carried out by three layers or five-layers corrugated fiberboard it is simple and exquisite packaging, in corrugated case or
Beautiful colorful figure and picture are printed in the surface of corrugated paper box, and this not only protects the commodity of inherence, and to packaging
Commodity serve publicity and beautification function.And seven layers or eleventh floor corrugated board be mainly used as electromechanics, flue-cured tobacco, furniture, motorcycle,
White goods etc. make packing case；In specific commodity, it can be combined with this corrugated board and inside and outside casing is made, be easy to
Make and beneficial to splendid attire, storage and the transport of commodity.With the needs of environmental protection and the requirement of national relevant policies, this kind of corrugated paper
The commodity packaging that plate makes, there is the trend of gradually substitution wooden-box package.
At present, the production of corrugated paper or corrugated board is persistently being improved with preparation technology, gradually from high grammes per square metre to
Low grammes per square metre direction is developed；And wood pulp is preferentially replaced using waste paper, the paper strength of gained is poor even so and hygroscopicity value is high；
Further, since there is internal sizing variable factor it is more caused by paper quality is unstable, class is difficult the problem of raising,
Most of manufacturer uses or abandoned less internal sizing, then the technique made up using top sizing is become as prevalence
Gesture.
For above-mentioned top sizing process, correspondingly have in production technology to sizing agent claimed below：A) effectively carry
High ring-pressure strength；B) Cobb values are significantly reduced（Hygroscopicity value）；C) it is fast to cure speed, it is desirable to which lower machine is with regard to ripe.It is however, existing on the market
Though the most Cypres having can improve the ring crush intensity of corrugated paper to a certain extent, sizing agent often be present
Dosage is big and the problem of cost is high.
In the prior art, such as a kind of sizing agent disclosed in Chinese patent CN102660899A, although curing speed is fast,
And do not get damp, but be the failure to significantly improve the ring crush intensity of corrugated paper.
Therefore, develop it is a kind of can either effectively improve the ring crush intensity of corrugated paper, and significantly reduce Cobb values, and can is enough
Ensure to cure fireballing corrugated paper Cypres, be one of emphasis that those skilled in the art currently research and develop.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, applied it is contemplated that obtaining a kind of corrugated paper with surface
Cobb values, and energy rapid aging can be not only greatly reduced in jelly, the Cypres, and substantially lower machine is just ripe, and can apply
The ring crush intensity of corrugated paper is increased substantially in the case that jelly dosage is constant.
Therefore, the first aspect of the present invention provides a kind of preparation method of corrugated paper Cypres, including following
Step：
Corrugated paper is well mixed with Cypres base-material, cationic additive, that is, the corrugated paper surface is made
Sizing agent；Wherein, the usage amount of the corrugated paper Cypres base-material is 100 parts by weight, the cationic additive
Usage amount is 5 ~ 50 parts by weight；
Wherein, the preparation method of the corrugated paper Cypres base-material comprises the following steps：
By cationic monomer, siloxanes,（Methyl）Acrylic ester monomer,（Methyl）Styrene, initiator, acetic acid and water
Add into reaction vessel, carry out Raolical polymerizable, generate the corrugated paper Cypres base-material；
Wherein, the preparation method of the cationic additive comprises the following steps：
Alkyl ketene dimer is added into the aqueous solution of cationic emulsifier, is sufficiently stirred, emulsion dispersion is carried out, obtains
Obtain cationic additive.
In addition, measure according to the corrugated paper obtained by method made above with the solid content of Cypres be 15wt%~
45wt%, pH=1~6.
Preferably, in the corrugated paper with the preparation method of Cypres base-material, the weight of each component is such as
Under：
（Methyl）100 parts of styrene
（Methyl）20~100 parts of acrylic ester monomer
20~100 parts of cationic monomer
2~10 parts of siloxanes
0.3~5 part of initiator
2~10 parts of acetic acid
160~1785 parts of water.
Preferably, it is described in the corrugated paper with the preparation method of Cypres base-material（Methyl）Esters of acrylic acid
Monomer is selected from following any one or more：Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid
Isobutyl ester, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, EMA, methacrylic acid third
Ester, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, EHMA；The sun
Ion monomer is acrylic acid-N, TMSDMA N dimethylamine base ethyl ester and/or dimethylaminopropyl methacrylamide；The siloxanes is selected from
It is any one or more below：Vinyltrimethoxy silane, VTES, vinyl three（2- methoxyl group ethoxies
Base）Silane, γ-methacryloxypropyl trimethoxy silane, γ -- methacryloxypropyl three（β-trimethoxy
Ethoxysilane）；The initiator is selected from following any one or more：Dibenzoyl peroxide, peroxidized t-butyl perbenzoate,
Dilauroyl peroxide, the peroxidating -2- ethyl acid tert-butyl esters.
Preferably, the reaction temperature of Raolical polymerizable of the corrugated paper in the preparation method of Cypres base-material
Spend for 80~140 DEG C, the reaction time is 3~8 hours.
In addition, measuring and being with the solid content of Cypres base-material according to the corrugated paper obtained by method made above
15wt%~45wt%, pH=1~6.
Preferably, in the preparation method of the cationic additive, the weight of each component is as follows：
100 parts of alkyl ketene dimer
30~70 parts of cationic emulsifier
158~1000 parts of water.
Preferably, in above-mentioned preparation method, the cationic emulsifier is hexadecyltrimethylammonium chloride and/or ten
Eight alkyl trimethyl ammonium chlorides.
Preferably, in the preparation method of the cationic additive, reaction temperature is 70~95 DEG C, the reaction time 0.1
~1 hour, the rpm/min of mixing speed 600~3000.
The second aspect of the present invention provides a kind of corrugated paper Cypres, and it is as described in first aspect present invention
Preparation method is made.
The third aspect of the present invention provides a kind of answering for the corrugated paper Cypres described in second aspect of the present invention
With, it is characterised in that the corrugated paper is used for the surface treatment of fluting medium with Cypres.
Preferably, in above-mentioned application, the surface treatment is：By the corrugated paper Cypres together with starch
Top sizing is carried out to the fluting medium.
In the preparation method of corrugated paper Cypres provided by the present invention, inventor is had found on corrugated paper surface
Cationic additive is added in sizing agent base-material, the ring crush intensity of corrugated paper is unexpectedly greatly improved, is caused simultaneously
The Cobb values of corrugated paper are also decreased obviously；Also, the corrugated paper is placed 24 hours in the environment of relative humidity 95%, its ring
Compressive Strength declines unobvious.This is probably because corrugated paper Cypres base-material and cationic additive have certain association
Same-action, siloxanes can be with the adhesions between carboxyl reaction reinforcing fibre, and at the same time, alkyl ketene dimer can be same
The substantial amounts of hydroxy combining of fiber surface, improve the water-resistance of film forming.
In addition, inventor also found, using Cypres provided by the present invention together with starch it is enterprising in corrugated paper
Row top sizing, and when reducing starch dosage 24% ~ 28%, remain able to obtain the ring crush intensity for reaching requirement and Cobb values,
Therefore, the raw material when preparation method of corrugated paper Cypres provided by the present invention can substantially reduce applying glue（Starch）'s
Dosage, so as to effectively reduce industrial cost.
It is further known that corrugated paper provided by the present invention is that one kind can meet that paper for surface sizing will with Cypres
The high-performance asked, the product of environmental protection.The product carries out top sizing together with starch to fluting medium, not only can substantially reduce watt
The Cobb values of stupefied paper, accelerate curing speed, and the ring crush intensity of corrugated paper can be increased substantially.
Embodiment
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment party
Formula.
First aspect, there is provided a kind of preparation method of corrugated paper Cypres, comprise the following steps：
Corrugated paper is well mixed with Cypres base-material, cationic additive, that is, the corrugated paper surface is made
Sizing agent；Wherein, the usage amount of the corrugated paper Cypres base-material is 100 parts by weight, the cationic additive
Usage amount is 5 ~ 50 parts by weight；
Wherein, the preparation method of the corrugated paper Cypres base-material comprises the following steps：
By cationic monomer, siloxanes,（Methyl）Acrylic ester monomer,（Methyl）Styrene, initiator, acetic acid and water
Add into reaction vessel, carry out Raolical polymerizable, generate the corrugated paper Cypres base-material；
Wherein, the preparation method of the cationic additive comprises the following steps：
Alkyl ketene dimer is added into the aqueous solution of cationic emulsifier, is sufficiently stirred, emulsion dispersion is carried out, obtains
Obtain cationic additive.
In a preferred embodiment, in the corrugated paper with the preparation method of Cypres base-material, each component
Weight is as follows：
（Methyl）100 parts of styrene
（Methyl）20~100 parts of acrylic ester monomer
20~100 parts of cationic monomer
2~10 parts of siloxanes
0.3~5 part of initiator
2~10 parts of acetic acid
160~1785 parts of water.
In a preferred embodiment, it is described in the corrugated paper with the preparation method of Cypres base-material（First
Base）Acrylic ester monomer is selected from following any one or more：Methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid
N-butyl, isobutyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, EMA,
Propyl methacrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid
Different monooctyl ester；The cationic monomer is acrylic acid-N, TMSDMA N dimethylamine base ethyl ester and/or dimethylaminopropyl methacrylamide；
The siloxanes is selected from following any one or more：Vinyltrimethoxy silane, VTES, vinyl three
（2- methoxy ethoxies）Silane, γ-methacryloxypropyl trimethoxy silane, γ -- methacryloxypropyl
Three（β-trimethoxy Ethoxysilane）；The initiator is selected from following any one or more：Dibenzoyl peroxide, peroxidating
T-butyl perbenzoate, dilauroyl peroxide, the peroxidating -2- ethyl acid tert-butyl esters.
In a preferred embodiment, radical polymerization of the corrugated paper in the preparation method of Cypres base-material
The reaction temperature of reaction is 80~140 DEG C, and the reaction time is 3~8 hours.
In a preferred embodiment, in the preparation method of the cationic additive, the weight of each component
It is as follows：
100 parts of alkyl ketene dimer
30~70 parts of cationic emulsifier
158~1000 parts of water.
In a preferred embodiment, the cationic emulsifier is hexadecyltrimethylammonium chloride and/or octadecane
Base trimethyl ammonium chloride.
In a preferred embodiment, in the preparation method of the cationic additive, reaction temperature is 70~95 DEG C,
0.1~1 hour reaction time, the rpm/min of mixing speed 600~3000.
Second aspect, there is provided a kind of corrugated paper Cypres, it is as the preparation side described in first aspect present invention
Method is made.
The third aspect, there is provided a kind of application of the corrugated paper Cypres described in second aspect of the present invention, it is special
Sign is that the corrugated paper is used for the surface treatment of fluting medium with Cypres.
In a preferred embodiment, described be surface-treated is：By the corrugated paper Cypres together with starch
Top sizing is carried out to the fluting medium.
Embodiment 1
（1）The preparation of corrugated paper Cypres base-material：
A）By 100g styrene, 20g n-butyl acrylates, 20g acrylic acid-N, TMSDMA N dimethylamine base ethyl ester, 0.3g peroxidating
Dibenzoyl adds into container in the lump to be well mixed, and obtains mix monomer, standby；
B）161.47g deionized waters are warming up to 80 DEG C, it is standby；
C）With condenser, Dropping feeder, agitator, thermometer four-hole boiling flask in, first add step A）Gained
The 10% of mix monomer, 80 DEG C are warming up to, step A is added dropwise in stirring reaction after 10 minutes）The remaining mix monomer of gained, it is added dropwise
5 hours time, continue insulation 1 hour after completion of dropwise addition at 80 DEG C, add 10g acetic acid, 80 DEG C of stirring reactions add again after 1 hour
Enter step B）In hot water, be cooled to 95 DEG C, add 4g γ-methacryloxypropyl trimethoxy silane and continue to stir
Reaction 1 hour is mixed, is cooled to 35 DEG C, pH=1.15.Filtered through 100 mesh filter screens, obtain the corrugated paper Cypres base
Material, solid content 44.85wt%.
（2）The preparation of cationic additive：
A）With condenser, agitator, thermometer four-hole boiling flask in, add 100g alkyl ketene dimers, heating
To 70 DEG C, 20 minutes are incubated at 70 DEG C after melting completely, it is stand-by；
B）In implementation steps A）While, with condenser, agitator, thermometer another four-hole boiling flask in, add
Enter 30g OTACs and 158.9g deionized waters, be stirred well to and be completely dissolved, then heat to 70 DEG C simultaneously
Insulation；
C）By step B）In mixing speed be adjusted to 600rpm/min, and by step A）Gained fused mass is at 70 DEG C, in 5
It is slowly added in~10 minutes to step B）In the resulting OTAC aqueous solution, it is sufficiently stirred, at a high speed
It is scattered 0.1 hour；Then, mixing speed is reduced to 200 rpm/min, and is cooled to 25 DEG C, is filtered, is made through 100 mesh filter screens
The cationic additive, its solid content are 45.15wt%.
（3）The preparation of corrugated paper Cypres：
Obtained corrugated paper is added into four-hole boiling flask with Cypres base-material 200g and obtained cationic additive 50g
It is middle to mix 10 minutes, the corrugated paper Cypres, solid content 44.83wt%, pH=1.12 are made.
Embodiment 2
（1）The preparation of corrugated paper Cypres base-material：
A）By 100g methyl styrenes, 100g Isooctyl acrylate monomers, 100g dimethylaminopropyl methacrylamides, 5g mistakes
Oxidation t-butyl perbenzoate adds into container in the lump to be well mixed, and obtains mix monomer, standby；
B）1783g deionized waters are warming up to 100 DEG C, it is standby；
C）With condenser, Dropping feeder, agitator, thermometer four-hole boiling flask in, first add step A）Gained
The 20% of mix monomer, 140 DEG C are warming up to, step A is added dropwise in stirring reaction after 10 minutes）The remaining mix monomer of gained, it is added dropwise
1 hour time, continue insulation 0.5 hour after completion of dropwise addition at 140 DEG C, add 2g acetic acid, 140 DEG C of stirring reactions are after 20 minutes
Add step B）In hot water, be cooled to 95 DEG C, add 10g VTESs continue stirring reaction 30 divide
Clock, 25 DEG C are cooled to, pH=5.89.Filtered through 100 mesh filter screens, obtain the corrugated paper Cypres base-material, solid content
15.25wt%。
（2）The preparation of cationic additive：
A）With condenser, agitator, thermometer four-hole boiling flask in, add 100g alkyl ketene dimers, heating
To 95 DEG C, 20 minutes are incubated at 95 DEG C after melting completely, it is stand-by；
B）In implementation steps A）While, with condenser, agitator, thermometer another four-hole boiling flask in, add
Enter 70g hexadecyltrimethylammonium chlorides and 970g deionized waters, be stirred well to and be completely dissolved, then heat to 95 DEG C and protect
Temperature；
C）By step B）In mixing speed be adjusted to 3000 rpm/min, and by step A）Gained fused mass at 95 DEG C,
In being slowly added in 5~10 minutes to step B）In the resulting hexadecyltrimethylammonium chloride aqueous solution, it is sufficiently stirred, it is high
Speed is scattered 1 hour；Then, mixing speed is reduced to 200 rpm/min, and is cooled to 25 DEG C, is filtered, is made through 100 mesh filter screens
The cationic additive, its solid content are 15.14wt%.
（3）The preparation of corrugated paper Cypres：
Obtained corrugated paper is added into four-hole boiling flask with Cypres base-material 200g and obtained cationic additive 20g
It is middle to mix 10 minutes, the corrugated paper Cypres, solid content 15.16wt%, pH=5.95 are made.
Embodiment 3
（1）The preparation of corrugated paper Cypres base-material：
A）By 100g methyl styrenes, 60g EMAs, 50g dimethylaminopropyl methacrylamides, 3g mistakes
Oxidation -2- ethyl acids the tert-butyl ester adds into container in the lump to be well mixed, and obtains mix monomer, standby；
B）505.5g deionized waters are warming up to 100 DEG C, it is standby；
C）With condenser, Dropping feeder, agitator, thermometer four-hole boiling flask in, first add step A）Gained
The 15% of mix monomer, 110 DEG C are warming up to, step A is added dropwise in stirring reaction after 10 minutes）The remaining mix monomer of gained, it is added dropwise
Time 2 h, continue at 110 DEG C insulation 1 hour after completion of dropwise addition, add 5g acetic acid, 110 DEG C of stirring reactions after 40 minutes again
Add step B）In hot water, be cooled to 95 DEG C, add 5g vinyltrimethoxy silanes and continue stirring reaction 1 hour, it is cold
But to 25 DEG C, pH=3.38.Filtered through 100 mesh filter screens, obtain the corrugated paper Cypres base-material, solid content
30.24wt%。
（2）The preparation of cationic additive：
A）With condenser, agitator, thermometer four-hole boiling flask in, add 100g alkyl ketene dimers, heating
To 85 DEG C, 20 minutes are incubated at 85 DEG C after melting completely, it is stand-by；
B）In implementation steps A）While, with condenser, agitator, thermometer another four-hole boiling flask in, add
Enter 50g OTACs and 350g deionized waters, be stirred well to and be completely dissolved, then heat to 85 DEG C and protect
Temperature；
C）By step B）In mixing speed be adjusted to 2000 rpm/min, and by step A）Gained fused mass at 85 DEG C,
In being slowly added in 5~10 minutes to step B）In the resulting OTAC aqueous solution, it is sufficiently stirred, it is high
Speed is scattered 0.5 hour；Then, mixing speed is reduced to 200 rpm/min, and is cooled to 25 DEG C, is filtered through 100 mesh filter screens, system
The cationic additive is obtained, its solid content is 30.37wt%.
（3）The preparation of corrugated paper Cypres：
Obtained corrugated paper is added into four-hole boiling flask with Cypres base-material 200g and obtained cationic additive 30g
It is middle to mix 10 minutes, the corrugated paper Cypres, solid content 30.21wt%, pH=3.09 are made.
Embodiment 4
（1）The preparation of corrugated paper Cypres base-material：
A）By 50g methyl styrenes, 50g styrene, 20g Isobutyl methacrylates, 20g methyl methacrylates, 30g
Dimethylaminopropyl methacrylamide, 50g acrylic acid-N, TMSDMA N dimethylamine base ethyl ester, 2g dilauroyl peroxides add in the lump
It is well mixed into container, obtains mix monomer, it is standby；
B）665g deionized waters are warming up to 100 DEG C, it is standby；
C）With condenser, Dropping feeder, agitator, thermometer four-hole boiling flask in, first add step A）Gained
The 15% of mix monomer, 100 DEG C are warming up to, step A is added dropwise in stirring reaction after 10 minutes）The remaining mix monomer of gained, it is added dropwise
3 hours time, continue at 100 DEG C insulation 1 hour after completion of dropwise addition, add 7g acetic acid, 100 DEG C of stirring reactions after 30 minutes again
Add step B）In hot water, be cooled to 95 DEG C, add 2g vinyl three（2- methoxy ethoxies）It is anti-that silane continues stirring
Answer 2 hours, be cooled to 25 DEG C, pH=2.85.Filtered through 100 mesh filter screens, obtain the corrugated paper Cypres base-material, Gu
Content 25.27wt%.
（2）The preparation of cationic additive：
A）With condenser, agitator, thermometer four-hole boiling flask in, add 100g alkyl ketene dimers, heating
To 90 DEG C, 20 minutes are incubated at 90 DEG C after melting completely, it is stand-by；
B）In implementation steps A）While, with condenser, agitator, thermometer another four-hole boiling flask in, add
Enter 60g hexadecyltrimethylammonium chlorides and 480g deionized waters, be stirred well to and be completely dissolved, then heat to 90 DEG C and protect
Temperature；
C）By step B）In mixing speed be adjusted to 1000 rpm/min, and by step A）Gained fused mass at 90 DEG C,
In being slowly added in 5~10 minutes to step B）In the resulting hexadecyltrimethylammonium chloride aqueous solution, it is sufficiently stirred, it is high
Speed is scattered 0.8 hour；Then, mixing speed is reduced to 200 rpm/min, and is cooled to 25 DEG C, is filtered through 100 mesh filter screens, system
The cationic additive is obtained, its solid content is 25.19wt%.
（3）The preparation of corrugated paper Cypres：
Obtained corrugated paper is added into four-hole boiling flask with Cypres base-material 200g and obtained cationic additive 20g
It is middle to mix 10 minutes, the corrugated paper Cypres, solid content 25.18wt%, pH=4.03 are made.
Application Example
The sizing agent prepared according to method disclosed in Chinese patent CN102660899A（Solid content is diluted to deionized water
15wt%）As a comparison case.
In addition, preparing sizing agent according to above-described embodiment 1 ~ 4, and solid content 15wt% is diluted to deionized water.
The configuration of glue application solution：The 500g 10wt% oxidized starch aqueous solution is prepared, is warming up to 90 DEG C, is gelatinized 20 minutes, drop
Temperature is to 40 DEG C, then is separately added into comparative example and sizing agent made from embodiment 1~4（Oxidized starch（It is dry）：Sizing agent（It is wet）=50：
4）, add water and be diluted to 8wt%.
Then, respectively by each glue application solution containing sizing agent made from comparative example and embodiment 1~4 in 120g fluting mediums
On be coated with 10# spreading rods, coating weight 2g/m2, dry 30 seconds or 120 seconds, take in 110 DEG C of baking ovens respectively after coating
Go out, be cooled to room temperature, and carry out following detect：
Cobb values determine：
GB/T 1540- suddenly can be pressed by absorbability analyzer using the XSH types of Hangzhou Qingtong Boke Automation Technology Co., Ltd.
1989 methods detect pattern to be measured.
Ring crush intensity determines：
Pattern to be measured is detected using the CT300A compressive strengths tester of Hangzhou Qingtong Boke Automation Technology Co., Ltd..
Specific testing result see the table below 1, wherein, Cobb values are more low, show that hygroscopicity value is lower, ring crush index gets over Gao Zebiao
Bright intensity is bigger：
Further, above-mentioned test pattern is placed 24 hours again with same method by inventor under 95% damp condition
Survey Cobb values and ring crush intensity, testing result are as shown in table 2 below：
By the data in Tables 1 and 2, using sizing agent made from the embodiment of the present invention 1 ~ 4 compared with comparative example,
Rapid aging is not only able to, increases substantially the ring crush intensity of corrugated paper, Cobb values are greatly reduced, moreover, in wet condition,
Cobb value value addeds are smaller, and ring crush intensity decreasing value is also smaller, and this shows that Cypres provided by the present invention also have very
Strong anti-performance of getting damp.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of preparation method of corrugated paper Cypres, comprises the following steps：
Corrugated paper is well mixed with Cypres base-material, cationic additive, that is, the corrugated paper top sizing is made
Agent；Wherein, the usage amount of the corrugated paper Cypres base-material is 100 parts by weight, the use of the cationic additive
Measure as 5 ~ 50 parts by weight；Characterized in that,
The preparation method of the corrugated paper Cypres base-material comprises the following steps：
By cationic monomer, siloxanes,（Methyl）Acrylic ester monomer,（Methyl）Styrene, initiator, acetic acid and water add
Into reaction vessel, Raolical polymerizable is carried out, generates the corrugated paper Cypres base-material；
The preparation method of the cationic additive comprises the following steps：
Alkyl ketene dimer is added into the aqueous solution of cationic emulsifier, is sufficiently stirred, carries out emulsion dispersion, obtains sun
Ionic additive.
2. preparation method according to claim 1, it is characterised in that the system in the corrugated paper with Cypres base-material
In Preparation Method, the weight of each component is as follows：
（Methyl）100 parts of styrene
（Methyl）20~100 parts of acrylic ester monomer
20~100 parts of cationic monomer
2~10 parts of siloxanes
0.3~5 part of initiator
2~10 parts of acetic acid
160~1785 parts of water.
3. preparation method according to claim 1, it is characterised in that described（Methyl）Acrylic ester monomer is selected from following
It is any one or more：Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, propylene
Tert-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, EMA, propyl methacrylate, methacrylic acid
N-butyl, Isobutyl methacrylate, Tert-butyl Methacrylate, EHMA；The cationic monomer is third
Olefin(e) acid-N, TMSDMA N dimethylamine base ethyl ester and/or dimethylaminopropyl methacrylamide；The siloxanes be selected from it is following any or
It is a variety of：Vinyltrimethoxy silane, VTES, vinyl three（2- methoxy ethoxies）Silane, γ-first
Base acryloxypropyl trimethoxy silane, γ -- methacryloxypropyl three（β-trimethoxy Ethoxysilane）；
The initiator is selected from following any one or more：Dibenzoyl peroxide, peroxidized t-butyl perbenzoate, the bay of peroxidating two
Acyl, the peroxidating -2- ethyl acid tert-butyl esters.
4. preparation method according to claim 1, it is characterised in that the preparation of corrugated paper Cypres base-material
The reaction temperature of Raolical polymerizable in method is 80~140 DEG C, and the reaction time is 3~8 hours.
5. preparation method according to claim 1, it is characterised in that in the preparation method of the cationic additive,
The weight of each component is as follows：
100 parts of alkyl ketene dimer
30~70 parts of cationic emulsifier
150~1000 parts of water.
6. preparation method according to claim 1, it is characterised in that the cationic emulsifier is cetyl trimethyl
Ammonium chloride and/or OTAC.
7. preparation method according to claim 1, it is characterised in that in the preparation method of the cationic additive,
Reaction temperature is 70~95 DEG C, 0.1~1 hour reaction time, the rpm/min of mixing speed 600~3000.
8. a kind of corrugated paper Cypres, it is characterised in that it is as according to the preparation any one of claim 1-7
Method is made.
9. a kind of application of corrugated paper Cypres according to claim 8, it is characterised in that the corrugated paper is used
Cypres are used for the surface treatment of fluting medium.
10. application according to claim 9, it is characterised in that the surface treatment is：The corrugated paper is applied with surface
Jelly carries out top sizing together with starch to the fluting medium.
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| CN107354811A (en) * | 2017-06-30 | 2017-11-17 | 常州瑞坦商贸有限公司 | A kind of preparation method of corrugated paper ring pressure strengthening agent |
| CN107338677A (en) * | 2017-07-24 | 2017-11-10 | 佛山金盛联合纸业有限公司 | A kind of corrugated paper Cypres and preparation method thereof |
| CN108383944B (en) * | 2018-01-17 | 2020-07-03 | 寿光美伦纸业有限责任公司 | Preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion |
| CN108642959A (en) * | 2018-05-09 | 2018-10-12 | 上海昶法新材料有限公司 | A kind of lignin Cypres and preparation method thereof |
| CN108532362A (en) * | 2018-05-09 | 2018-09-14 | 上海昶法新材料有限公司 | A kind of lignin sizing agent and preparation method thereof |
| CN110485196A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | Biological surface sizing agent |
| CN110485200A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | A kind of biomass sizing agent and preparation method thereof |
| CN110485197A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | Biomass sizing agent |
| CN110485201A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | A kind of lignin Cypres and preparation method thereof |
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| CN102011343B (en) * | 2010-06-29 | 2012-07-04 | 上海东升新材料有限公司 | Surface sizing agent for corrugated paper as well as preparation method and application thereof |
| CN102086614B (en) * | 2010-08-25 | 2012-11-14 | 永港伟方（北京）科技股份有限公司 | Surface sizing agent as well as preparation method and application thereof |
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