CN108642955A - A kind of waterproof paper and preparation method thereof - Google Patents

A kind of waterproof paper and preparation method thereof Download PDF

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Publication number
CN108642955A
CN108642955A CN201810317096.2A CN201810317096A CN108642955A CN 108642955 A CN108642955 A CN 108642955A CN 201810317096 A CN201810317096 A CN 201810317096A CN 108642955 A CN108642955 A CN 108642955A
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CN
China
Prior art keywords
monomer
paper
waterproof
fluorine
containing acrylate
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.)
Pending
Application number
CN201810317096.2A
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Chinese (zh)
Inventor
郭惠霞
李晨
毛小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwest Normal University
Original Assignee
Northwest Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Northwest Normal University filed Critical Northwest Normal University
Priority to CN201810317096.2A priority Critical patent/CN108642955A/en
Publication of CN108642955A publication Critical patent/CN108642955A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/22—Esters containing halogen
    • C08F120/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • 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

Abstract

The present invention discloses a kind of waterproof paper, including paper and the waterproof membrane for being deposited on paper surface, and the waterproof membrane is fluorine-containing acrylate polymer.The waterproof paper is by including the following steps to obtain (1) by fluorine-containing acrylate monomer gasification；(2) monomer of gasification is sent into plasma reactor, plasma polymerization occurs under glow discharge for monomer, and the polymer deposits of generation form waterproof membrane in paper surface.Compared with prior art, waterproof paper of the invention has good hydrophobicity, and production operation process is simple, and reduces chemical kind and dosage used in paper water-proofing treatment.

Description

A kind of waterproof paper and preparation method thereof
Technical field
The invention belongs to functional paper fields, and in particular to a kind of waterproof paper and preparation method thereof.
Background technology
Paper is made of plant fiber, and plant fiber is one of the natural resources being most easy to get extensively at present.It is made from it Paper have many advantages, such as such as：It is renewable, of low cost, derive from a wealth of sources and be conveniently easy to get, be biodegradable environmental-friendly, nontoxic etc. Advantage is widely applied to printing, writing, packaging material, modification and protectiveness material etc. by people.But due to plant fibre Tieing up the paper that its hydrophilic person's character is made from it equally has good hydrophily, this just greatly constrains the application of paper.Cause This preparation and application with water-proof function paper is just particularly important.
In addition, the widest packaging material used in market is made to environment made of nondegradable plastics now At huge irreversible destruction, also increasingly paid attention to government by society with the development environment problem of society, use is nontoxic The plastics packaging material that the degradable paper package of evil replaces traditional harmfulness larger is imperative.
The existing method for improving paper products water proofing property mainly has sizing, surface coating, fiber to connect technological transformation etc., these tradition The deficiency of method is that chemicals usage and type are excessive.
Low temperature plasma polymerization is by penetrating as a kind of simple for process, convenient and efficient, clean surface treatment method Frequency low pressure glow discharge, the energy generated is about 5eV, can cause the fracture of molecule covalent key (4eV).Utilize plasma In electronics, particle, free radical and other excited state molecule isoreactivity particles make monomer polymerization.
Invention content
The purpose of the present invention is to provide a kind of waterproof papers.
Another object of the present invention is to provide a kind of methods preparing above-mentioned waterproof paper using plasma polymerization techniques.
In order to solve the above technical problem, the present invention provides the following technical solutions：
A kind of waterproof paper, including paper and the waterproof membrane for being deposited on paper surface, the waterproof membrane are fluorine-containing acrylic acid Ester polymer.
Preferably, the fluorine-containing acrylate polymer by fluorine-containing acrylate monomer through plasma polymerization Deposition obtains.
Preferably, the chemical formula of the fluorine-containing acrylate monomer is as follows：CH2=CHCOO (CH2)mCnF2n+1, wherein m =0~3, n=5~10, it is specific such as 1H, 1H, 2H, 2H- perfluoro decyls acrylate, 1H, 1H- perfluoro capryl acrylate etc..
Preferably, the static contact angle of the waterproof paper is 100 °~160 °.
The preparation method of above-mentioned waterproof paper, includes the following steps：
(1) fluorine-containing acrylate monomer is gasified；
(2) monomer of gasification is sent into plasma reactor, under glow discharge plasma polymerization occurs for monomer The polymer deposits of reaction, generation form waterproof membrane in paper surface.
Preferably, in step (2), the pressure of plasma reactor is 25~40mTorr, the flow of monomer is 5~ 9sccm, discharge power are 20~35W, and polymerization reaction time is 60~2400s.
Preferably, the glow discharge is radio frequency glow discharge.
Preferably, the fluorine-containing acrylate monomer is 1H, 1H, 2H, 2H- perfluoro decyl acrylate, polymerisation Time is 500~2400s, and the static contact angle of the waterproof paper obtained can reach 130 ° or more.
The fluorine-containing acrylate monomer of the present invention generates low temperature plasma by glow discharge, and using in plasma Electronics, particle, free radical and other excited state molecule isoreactivity particles so that monomer is polymerize, to being obtained in paper surface To one layer of micron order or nano level waterproof layer.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings：
Fig. 1 is static contact angle of the water droplet in waterproof paper；
Fig. 2 (a) is the SEM photograph on body paper surface, (b) SEM photograph on waterproof paper surface；
Fig. 3 is Infrared spectra adsorption spectrogram.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Common print paper, brown paper, toilet paper, package paper etc. may be used as body paper in the present invention.
Embodiment 1
Pending body paper is lain in into plasma reactor (Europlasma CD400, radio frequency glow discharge) work On the objective table of intracavitary, it is 40mTorr to vacuumize the pressure in working chamber.
By 1H, 1H, 2H, 2H- perfluoro decyls acrylate (CAS 27905-45-9) heating becomes gas at 150 DEG C State uses helium to bring gaseous monomer in the working chamber of plasma reactor into as carrier gas, and flow of monomer is arranged in 9sccm, In the case where discharge power is 35W monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing third on body paper surface Olefine acid ester polymer layer (Infrared spectra adsorption spectrogram such as Fig. 3), aggregation deposition time 2400s.
(water) static contact angle of waterproof paper obtained by the present embodiment is 133 °.
Embodiment 2
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 40mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 8sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 140 °.
Embodiment 3
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 8sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 145 °.
Embodiment 4
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 25mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 8sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 140 °.
Embodiment 5
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 7sccm, the handle in the case where discharge power is 20W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 148 °.
Embodiment 6
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 7sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 151 °.
Embodiment 7
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 6sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 153 °.
Embodiment 8
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 5sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 153 °.
Embodiment 9
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 5sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 60s.
The static contact angle of waterproof paper obtained by the present embodiment is 103 °.
Embodiment 10
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 5sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 120s.
The static contact angle of waterproof paper obtained by the present embodiment is 115 °.
Embodiment 11
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 5sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 500s.
The static contact angle of waterproof paper obtained by the present embodiment is 132 °.
Embodiment 12
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H, 2H, the heating of 2H- perfluoro decyl acrylate becomes gaseous state at 150 DEG C, uses helium will as carrier gas Gaseous monomer is brought into the working chamber of plasma reactor, and flow of monomer setting is in 5sccm, the handle in the case where discharge power is 25W Monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylate polymer layer on body paper surface, polymerization Sedimentation time 1000s.
The static contact angle of waterproof paper obtained by the present embodiment is 140 °.
Embodiment 13
Pending body paper is lain on the objective table in plasma reactor working chamber, is vacuumized in working chamber Pressure is 30mTorr.
By 1H, 1H- perfluoro capryls acrylate (CAS 307-98-2) heating becomes gaseous state at 150 DEG C, uses helium Gaseous monomer is brought into the working chamber of plasma reactor as carrier gas, flow of monomer is arranged in 5sccm, in discharge power For under 25W monomer plasma, you can aggregation deposition forms hydrophobic fluorine-containing acrylic ester polymerization on body paper surface Nitride layer, aggregation deposition time 2400s.
The static contact angle of waterproof paper obtained by the present embodiment is 103 °.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's Within protection domain.

Claims (10)

1. a kind of waterproof paper, including paper and the waterproof membrane for being deposited on paper surface, the waterproof membrane is fluorine-containing acrylate Polymer.
2. waterproof paper according to claim 1, it is characterised in that：The fluorine-containing acrylate polymer is by fluorine-containing third Olefin(e) acid ester monomer deposits to obtain through plasma polymerization.
3. waterproof paper according to claim 2, it is characterised in that：The chemical formula of the fluorine-containing acrylate monomer is such as Under：CH2=CHCOO (CH2)mCnF2n+1, wherein m=0~3, n=5~10.
4. waterproof paper according to claim 3, it is characterised in that：The fluorine-containing acrylate monomer be 1H, 1H, 2H, 2H- perfluoro decyls acrylate, 1H, 1H- perfluoro capryl acrylate.
5. waterproof paper according to claim 1, it is characterised in that：The static contact angle of the waterproof paper be 100 °~ 160°。
6. the preparation method of waterproof paper described in claim 1, includes the following steps：
(1) fluorine-containing acrylate monomer is gasified；
(2) monomer of gasification is sent into plasma reactor, under glow discharge plasma polymerization occurs for monomer, The polymer deposits of generation form waterproof membrane in paper surface.
7. preparation method according to claim 6, it is characterised in that：In step (2), the pressure of plasma reactor is The flow of 25~40mTorr, monomer are 5~9sccm, and discharge power is 20~35W, and polymerization reaction time is 60~2400s.
8. preparation method according to claim 6, it is characterised in that：The glow discharge is radio frequency glow discharge.
9. preparation method according to claim 6, it is characterised in that：The chemical formula of the fluorine-containing acrylate monomer is such as Under：CH2=CHCOO (CH2)mCnF2n+1, wherein m=0~3, n=5~10.
10. waterproof paper according to claim 6, it is characterised in that：The fluorine-containing acrylate monomer be 1H, 1H, 2H, 2H- perfluoro decyls acrylate, 1H, 1H- perfluoro capryl acrylate.
CN201810317096.2A 2018-04-10 2018-04-10 A kind of waterproof paper and preparation method thereof Pending CN108642955A (en)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074989A (en) * 2022-08-01 2022-09-20 武汉纺织大学 Super-hydrophobic Lyocell fabric and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2956676A1 (en) * 2010-02-25 2011-08-26 Antoine Boutiron METHOD FOR OBTAINING A SAFE FOR PROTECTING THE SURFACES TO BE BUILT AGAINST INSECTS AND IN PARTICULAR THE TERMITES
CN103468835A (en) * 2013-09-16 2013-12-25 四川大学 Waterproof leather prepared via polymerization deposition of low-temperature plasmas and preparation method of waterproof leather
CN103946286A (en) * 2011-07-21 2014-07-23 P2I有限公司 Surface coatings
CN105524221A (en) * 2014-10-23 2016-04-27 中国制浆造纸研究院 Preparation method of plasma-triggered fluorine-carbon oil-resistance and water-resistance paper
CN107653744A (en) * 2017-09-12 2018-02-02 成都新柯力化工科技有限公司 A kind of ultra-hydrophobic paper and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2956676A1 (en) * 2010-02-25 2011-08-26 Antoine Boutiron METHOD FOR OBTAINING A SAFE FOR PROTECTING THE SURFACES TO BE BUILT AGAINST INSECTS AND IN PARTICULAR THE TERMITES
CN103946286A (en) * 2011-07-21 2014-07-23 P2I有限公司 Surface coatings
CN103468835A (en) * 2013-09-16 2013-12-25 四川大学 Waterproof leather prepared via polymerization deposition of low-temperature plasmas and preparation method of waterproof leather
CN105524221A (en) * 2014-10-23 2016-04-27 中国制浆造纸研究院 Preparation method of plasma-triggered fluorine-carbon oil-resistance and water-resistance paper
CN107653744A (en) * 2017-09-12 2018-02-02 成都新柯力化工科技有限公司 A kind of ultra-hydrophobic paper and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074989A (en) * 2022-08-01 2022-09-20 武汉纺织大学 Super-hydrophobic Lyocell fabric and preparation method thereof
CN115074989B (en) * 2022-08-01 2023-11-24 武汉纺织大学 Super-hydrophobic lyocell fabric and preparation method thereof

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Application publication date: 20181012