CN1033066A - Modified polyvinyl acetate emulsion - Google Patents

Modified polyvinyl acetate emulsion Download PDF

Info

Publication number
CN1033066A
CN1033066A CN 87107890 CN87107890A CN1033066A CN 1033066 A CN1033066 A CN 1033066A CN 87107890 CN87107890 CN 87107890 CN 87107890 A CN87107890 A CN 87107890A CN 1033066 A CN1033066 A CN 1033066A
Authority
CN
China
Prior art keywords
concentration
emulsion
pva
weight
cement
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
CN 87107890
Other languages
Chinese (zh)
Inventor
郑佳宝
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.)
ZHEJIANG POLYTECHNICAL COLLEGE
Original Assignee
ZHEJIANG POLYTECHNICAL COLLEGE
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 ZHEJIANG POLYTECHNICAL COLLEGE filed Critical ZHEJIANG POLYTECHNICAL COLLEGE
Priority to CN 87107890 priority Critical patent/CN1033066A/en
Publication of CN1033066A publication Critical patent/CN1033066A/en
Pending legal-status Critical Current

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention is a kind of aqueous binders, mainly is made up of institutes such as VAc, DBP, PVA, formaldehyde, urea, phosphoric acid.Be specially adapted to animality and vegetative fiber material (as timber, paper, leather, cotton wool fabric etc.), cement, pottery, asbestos and porous plastics etc., have good binding property and water tolerance.Also can be widely used in stickup, preparation architectural latex coating, the moulding sand for casting coating of combination, the buildings inside/outside decorative material of bonding, non-woven cementation, insulation and the sound-absorbing material of unsewn binding, cotton fabric starching, bamboo wood furniture and the artwork thereof of books, the intensity and the elasticity of refinforced cement, and as the dispersion agent of fluorescent-lamp fluorescent powder etc.

Description

Modified polyvinyl acetate emulsion
The present invention is a kind of water-soluble binder, is specially adapted to the unsewn binding of animality and vegetative fiber material (as timber, paper, leather, cotton wool fabric etc.), cement, pottery, bamboo wood furniture and artwork thereof, book etc.
Before the present invention made, in the letex polymerization of vinyl acetate (VAC), polyvinyl alcohol (PVA) had the dual function of protective colloid and emulsifying agent concurrently.Under the certain prerequisite of consumption, the polymerization degree of PVA has very big influence to the viscosity of polyvinyl acetate (PVA) (PVAC) emulsion, and the polymerization degree is higher, and then the viscosity of emulsion is bigger.The general polymerization degree that all adopts is 1700 PVA.Alcoholysis degree is 99.5% polyvinyl alcohol (be as the home-made specification 17~99 PVA), because the ethanoyl (CH in the molecular structure 3COO-) (OH) replaced by hydroxyl basically.Therefore, the texture ratio of PVA molecular chain is more regular, and crystallinity is bigger, and its aqueous solution (solid content 5~10%) just is easy to form jelly , And and dense more easy freezing more at 5~10 ℃.Synthetic PVAC emulsion frost resistance and freeze-thaw stability are all very poor in such PVA aqueous solution, i.e. emulsion very easy breakdown of emulsion and scrapping after freezing.If adopting alcoholysis degree is that 88%(such as home-made specification are the PVA of 17-88) polyvinyl alcohol; owing to kept a part of ethanoyl on its molecular chain; make the PVA molecule have the part unsymmetrical structure group different with polarity; destroyed the regularity of molecular structure to a certain extent; therefore crystallinity is less; emulsifying effectiveness is also better than the PVA of 17-99, and its freeze-thaw stability of the emulsion of making, frost resistance all slightly improve, but the water tolerance of dehydration film becomes poorer.In traditional synthesis technique, normally the polyvinyl alcohol of two kinds of specifications respectively adopts half, but can not fundamentally improve the performance of emulsion.
Polyvinyl acetate (PVA) is a thermoplastic resin, softening temperature is low, adds the PVA that has adopted water tolerance very poor in the manufacturing processed, so emulsion has two deadly defects of poor heat resistance and poor water resistance, place restrictions on its use range, reduced its use value.
If make PVA and formaldehyde or butyraldehyde condensation,, improve the emulsifying property of PVA and the frost resistance and the water tolerance of raising PVAC emulsion to improve the irregularity of molecular structure.But the consumption of formaldehyde or butyraldehyde can not use too much, otherwise the water-soluble variation of polyvinyl acetal, in addition, this acetal product has the raising along with its degree of acetalization, and it is big that the solubleness in cold water becomes, the evident characteristic that solubleness diminishes in hot water.For example, press PVA: CH 2O(36%)=and 100: 40 ratio synthetic polyvinyl formal solution (~10%), opalescence is appearring more than 60 ℃, begin to separate out solid more than 70 ℃.And the letex polymerization temperature of PVAc is at 78~90 ℃.As adopt the modified product work of this polyvinyl alcohol to protect colloid, in case protective colloid is separated out from liquid phase in polymerization process, emulsion particle will lose the protection glue-line, interparticle cohesion take place then cause the polymerization failure.So the condensation of general carboxaldehyde radicals is below 20%, the butyraldehyde base only can condensation about 3~5%, even like this except the emulsifying property that has improved PVA, the raising of emulsion property is not had tangible effect.
Task of the present invention provides a kind of frost resistance, freeze-thaw stability and water-tolerant, the modified polyvinyl acetate emulsion that thermotolerance is high.
This emulsion is by protective colloid 62.4~67.8%(weight), vinyl acetate (VAc) 27.5~32.1%(weight) and other subsidiary material formed.
Protective colloid is by polyvinyl alcohol (PVA) 7.82~8.74%(weight), 36%(concentration) formaldehyde 8.50~9.10%(weight), 31%(concentration) hydrochloric acid 0.34~0.55%(weight), 85%(concentration) phosphoric acid 0.87~1.56%(weight), 10%(concentration) sodium hydroxide 1.70~2.18%(weight), urea 1.36~1.82%(weight) and the water of equal amount formed.
Other subsidiary material in the emulsion are by emulsifying agent (OP-10) 0.30~0.35%(weight), initiator 10%(concentration) ammonium persulphate 0.54~0.63%(weight), neutralizing agent 10%(concentration) sodium bicarbonate 0.90~1.05%(weight), plasticizer phthalic acid dibutylester (DBP) 3.0~3.5%(weight) institute form.
The present invention adopts phosphoric acid to make linking agent, thereby obtains a kind of water-soluble aqueous transparent colloid of high degree of acetalization when utilizing formaldehyde and polyvinyl alcohol to carry out condensation to make protective colloid.This colloid itself just has high adhesive property, emulsifying property and anti-freezing property , And and solid does not take place between 80~95 ℃ and separate out owing to introduce polar groups in a large number on the PVA molecular chain.The more important thing is that its dehydration process under normal temperature (≤40 ℃) condition is a cross-linking process between the molecular chain, thereby its dehydration film is insoluble to boiling water, has water-soluble irreversible feature.Therefore, adopt the protective colloid of this colloid, can improve frost resistance, freeze-thaw stability and the water tolerance of PVAc emulsion greatly, improved the thermotolerance of polyvinyl acetate (PVA) simultaneously to a certain extent as synthetic PVAc emulsion.Thereby fundamentally solved existing weakness when adopting general water-soluble polymer to make the protection colloid.This binding agent can mix , And by arbitrary proportion with the PVAc emulsion can stable for extended periods of time.Modified polyvinyl acetate emulsion described later, its rate of drying are compared with pure PVAc emulsion with cohesive strength does not all have tangible gap.
Emulsion of the present invention has good binding property to animality and vegetative fiber material (as timber, paper, leather, cotton wool fabric etc.), cement, pottery, asbestos and porous plastics etc.Also can be widely used in the combination of bonding, non-woven cementation, insulation and the sound-absorbing material of unsewn binding, cotton fabric starching, bamboo wood furniture and the artwork thereof of book, the stickup of buildings inside/outside decorative material also can be used for preparing the intensity of architectural latex coating and moulding sand for casting coating, refinforced cement and elasticity and as the dispersion agent of fluorescent-lamp fluorescent powder etc.
Embodiment
Step 1: (preparation of protective colloid)
1, the water and the PVA that add formula ratio in reactor were insulated and stirred more than 90 ℃ 0.5 hour.
2, in reactor, slowly add dense HCl and H 3PO 4, make PH<3 of reactant.
3, with about 0.5 hour, while hot the formaldehyde of formula ratio is added drop-wise in the reactor, under normal pressure, keeps 80~85 ℃ then, stirring reaction 2 hours.
4, with 10%NaOH solution reactant PH is adjusted to 4~5, adds urea then, reaction is 1 hour under 80~85 ℃ of conditions.
5, with 10%NaOH the PH of reactant is adjusted to 8~8.5 again, is cooled to 40~60 ℃ of dischargings, be stored in the plastic tank, covered and enclosed, standby.
Technical indicator:
Outward appearance: the water-soluble colloid of the little yellow transparence of thickness
Solid content: 18.5~19.5%
PH value: 8~8.5
Viscosity:>4000 centipoises
Free aldehyde :≤1.5%
Congeal a little :-4~-5 ℃
Water tolerance: the anti-boiling water of normal temperature (≤40 ℃) dehydration film was not clamminess, does not dissolve more than 1 hour.
Step 2 (preparation of modified polyvinyl acetate emulsion)
1, protective colloid is put into reactor for 27.8~32.4 parts, open the water coolant of stirring and reflux exchanger.
2, add again (OP-10) 0.30~0.35 part, VAc monomer total amount 15% and initiator total amount 40%, close the material port lid, stir and heat up, occur during to 60~66 ℃ refluxing, reaction solution gradually is creamy white, temperature rises gradually.
3, when temperature is raised to 80~82 ℃, it is gradually few to reflux, and evenly dropwised remaining VAc monomer (account for total amount 85%) in~8 hours this moment, and temperature of reaction can be controlled in 78~82 ℃.When dripping monomer, added initiator one time every 1 hour, add altogether 8 times, each additional amount is 5% of an initiator total amount.
4, after monomer dropping finishes, remaining initiator (account for total amount 20%) is all added , And be warming up to 90~93 ℃ of stirring reaction half an hour, be cooled to then below 50 ℃.
5, add 10%NaHCO lentamente 30.90~1.05 parts, add 3.0~3.5 parts of DBP after stirring again and stirred 40 minutes.
6, get 30.0~40.0 parts of protective colloids in addition and add in the emulsion, stir and got final product discharging in 20 minutes.
Technical indicator:
Outward appearance: oyster white stiff glue
PH value: 4~6
Solid content: 42~48%
Viscosity:>4000 centipoises
Particle diameter :~1 micron
Congeal a little :-3~-4 ℃
Freeze thawing :-10 ℃ 12 hours~+ 23 ℃ 12 hours be a circulation, 5 the circulation every performance index constant.
The intensity of bonding timber :~80kg/cm 2
Use temperature: 0~40 ℃

Claims (2)

1, a kind of animal and plant filamentary material that is used for; agglutinating modified polyvinyl acetate emulsions such as cement, pottery, asbestos, porous plastics, book unsewn binding, cotton fabric starching, bamboo wood furniture and artwork thereof, non-woven fabrics, buildings inside/outside decorative material; contain protective colloid, vinyl acetate and other subsidiary material, it is characterized in that: (weight %)
Protective colloid 62.4~67.8%
Its composition is: polyvinyl alcohol 7.82~8.74%
(36% concentration) formaldehyde 8.50~9.10%
(31% concentration) hydrochloric acid 0.34~0.55%
(85% concentration) phosphoric acid 0.87~1.56%
(10% concentration) sodium hydroxide 1.70~2.18%
Urea 1.36~1.82%
Level is weighed
Vinyl acetate 27.5~32.1
And other subsidiary material.
2, by the described emulsion of claim 1, it is characterized in that other subsidiary material in the emulsion contain (weight %):
Emulsifying agent (OP-10) 0.30~0.35
(10% concentration) ammonium persulphate 0.54~0.63
(10 concentration) sodium bicarbonate 0.90~1.05
Dibutyl phthalate 3.0~3.5
CN 87107890 1987-11-13 1987-11-13 Modified polyvinyl acetate emulsion Pending CN1033066A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 87107890 CN1033066A (en) 1987-11-13 1987-11-13 Modified polyvinyl acetate emulsion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 87107890 CN1033066A (en) 1987-11-13 1987-11-13 Modified polyvinyl acetate emulsion

Publications (1)

Publication Number Publication Date
CN1033066A true CN1033066A (en) 1989-05-24

Family

ID=4816280

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 87107890 Pending CN1033066A (en) 1987-11-13 1987-11-13 Modified polyvinyl acetate emulsion

Country Status (1)

Country Link
CN (1) CN1033066A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295286C (en) * 2005-04-15 2007-01-17 宁波广用纳米涂料有限公司 Emulsion for environmental protection type latex paint and preparation method
CN100410438C (en) * 2005-09-23 2008-08-13 扬州市邗江无纺布厂 Abrasive felt process
CN100445497C (en) * 2002-12-27 2008-12-24 克里斯廷·E·沃尔纳 Cementitious veneer and laminate material
CN102219435A (en) * 2011-06-03 2011-10-19 浏阳市金仁竹木工艺品有限公司 Decorative surface slurry used for wood line printing process
CN103895274A (en) * 2012-12-29 2014-07-02 深圳富泰宏精密工业有限公司 Ceramic and plastic complex and preparation method thereof
CN104136557A (en) * 2011-12-07 2014-11-05 瓦克化学公司 Low formaldehyde and high wet strength fibrous nonwoven substrate treated with a vinyl acetate ethylene copolymer or a vinyl acetate polymer dispersion
CN104478334A (en) * 2014-12-12 2015-04-01 如皋市东陈镇爱红工艺品厂 Art craft with magnetism and plasticity and preparation method of art craft
CN104478335A (en) * 2014-12-12 2015-04-01 如皋市东陈镇爱红工艺品厂 Novel plastic handiwork and making method thereof
CN104479268A (en) * 2014-10-30 2015-04-01 东莞市智高文具有限公司 Nontoxic light-weight color mud and preparation method
CN104527301A (en) * 2014-12-12 2015-04-22 如皋市东陈镇爱红工艺品厂 Antibacterial plastic handicraft article and manufacturing method thereof
CN105945210A (en) * 2016-05-13 2016-09-21 欧振云 Binder for casting and preparation method thereof
CN108623736A (en) * 2017-03-17 2018-10-09 巨石集团有限公司 A kind of self-cross linking type polyvinyl acetate film forming agent and its preparation method and application

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100445497C (en) * 2002-12-27 2008-12-24 克里斯廷·E·沃尔纳 Cementitious veneer and laminate material
CN1295286C (en) * 2005-04-15 2007-01-17 宁波广用纳米涂料有限公司 Emulsion for environmental protection type latex paint and preparation method
CN100410438C (en) * 2005-09-23 2008-08-13 扬州市邗江无纺布厂 Abrasive felt process
CN102219435A (en) * 2011-06-03 2011-10-19 浏阳市金仁竹木工艺品有限公司 Decorative surface slurry used for wood line printing process
CN102219435B (en) * 2011-06-03 2012-12-05 浏阳市金仁竹木工艺品有限公司 Decorative surface slurry used for wood line printing process
CN104136557B (en) * 2011-12-07 2017-03-08 瓦克化学公司 The low formaldehyde content processing through vinyl acetate ethylene copolymers dispersion or vinyl acetate polymer dispersion and the fiber non-woven base material of high wet strength
CN104136557A (en) * 2011-12-07 2014-11-05 瓦克化学公司 Low formaldehyde and high wet strength fibrous nonwoven substrate treated with a vinyl acetate ethylene copolymer or a vinyl acetate polymer dispersion
CN103895274A (en) * 2012-12-29 2014-07-02 深圳富泰宏精密工业有限公司 Ceramic and plastic complex and preparation method thereof
CN103895274B (en) * 2012-12-29 2017-05-03 深圳富泰宏精密工业有限公司 Ceramic and plastic complex and preparation method thereof
US9855722B2 (en) 2012-12-29 2018-01-02 Shenzhen Futaihong Precision Industry Co., Ltd. Composite article and method for making same
CN104479268A (en) * 2014-10-30 2015-04-01 东莞市智高文具有限公司 Nontoxic light-weight color mud and preparation method
CN104478334A (en) * 2014-12-12 2015-04-01 如皋市东陈镇爱红工艺品厂 Art craft with magnetism and plasticity and preparation method of art craft
CN104478335A (en) * 2014-12-12 2015-04-01 如皋市东陈镇爱红工艺品厂 Novel plastic handiwork and making method thereof
CN104527301A (en) * 2014-12-12 2015-04-22 如皋市东陈镇爱红工艺品厂 Antibacterial plastic handicraft article and manufacturing method thereof
CN105945210A (en) * 2016-05-13 2016-09-21 欧振云 Binder for casting and preparation method thereof
CN108623736A (en) * 2017-03-17 2018-10-09 巨石集团有限公司 A kind of self-cross linking type polyvinyl acetate film forming agent and its preparation method and application
CN108623736B (en) * 2017-03-17 2020-08-25 巨石集团有限公司 Self-crosslinking polyvinyl acetate film-forming agent and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN1033066A (en) Modified polyvinyl acetate emulsion
US6102121A (en) Conformance improvement additive, conformance treatment fluid made therefrom, method of improving conformance in a subterranean formation
KR101331454B1 (en) Slow released fertilizer and preparation method thereof
CN102040928A (en) Modified waterproof frost-resisting white latex
JPH05186637A (en) Building material product containing organic polymer as thickening agent
CA2037214A1 (en) Moldings
JP4979192B2 (en) Aqueous polymer dispersions, their production and use, in particular anticorrosive coatings
DE50015710D1 (en) Aqueous coating agent, process for its preparation and its use
CN104293245A (en) Vinyl acetate wood adhesive and preparation method thereof
CN1377929A (en) Modified water resistant low temperature white emulsoid
US3433701A (en) Water resistant polyvinyl acetate adhesive compositions
CA1202438A (en) Modified vinyl acetate adhesives containing low temperature fusion aids
DE2138202A1 (en) Process for the production of aqueous graft and / or block copolymer emulsions
JPH06228519A (en) Rf curing type i wood adhesive composition comprising vinyl acetate/nma copolymer emulsion containing tetramethylol glycol uril
CA1226998A (en) Binders for building adhesives, troweling compounds and plasters, based on halogen-free emulsion copolymers of monoolefinically unsaturated carboxylates
CA1091376A (en) Vinyl chloride polymer latex based cement additives
CN108715757A (en) A kind of preparation method of acidproof thickening agent and its application in multifunctional acid and acid-resistant pressing crack liquid
CN109988529A (en) A kind of preparation method of water-resistant type polyvinyl acetate adiabatic gum
CN111944378A (en) Polymer-based waterproof film, preparation method and application thereof
GB2070026A (en) Priming compositions for a base of cement mortar or concrete
CN102532389B (en) Poly-vinyl versatate-vinyl acetate-ethylene emulsion and emulsion polymerization preparation method
US3098049A (en) Composition comprising reaction product of hydrolyzed vinyl acetate polymer and periodate oxidized polysaccharide and process for preparing same
CN102391408B (en) Synthesis method for preparing polyvinyl acetate/alpha-pinene copolymer emulsion by modifying nano attapulgite
CN104861218A (en) Compound chitin -potassium titanate crystal whisker membrane and preparation method thereof
KR0153865B1 (en) Waterproof polymer cement material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication