CN102391408B - Synthesis method for preparing polyvinyl acetate/alpha-pinene copolymer emulsion by modifying nano attapulgite - Google Patents
Synthesis method for preparing polyvinyl acetate/alpha-pinene copolymer emulsion by modifying nano attapulgite Download PDFInfo
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- CN102391408B CN102391408B CN201110183519.4A CN201110183519A CN102391408B CN 102391408 B CN102391408 B CN 102391408B CN 201110183519 A CN201110183519 A CN 201110183519A CN 102391408 B CN102391408 B CN 102391408B
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Abstract
The invention relates to polyvinyl acetate, in particular to a modified polyvinyl acetate copolymer emulsion prepared by adopting nano particles, which solves the problem of formaldehyde pollution in the production of the existing polyvinyl acetate.
Description
Technical field
The present invention is a kind of preparing polyvinyl acetate/alpha-pinene copolymer emulsion through modification of nano-attapulgite synthetic method, belongs to processed and applied and the sizing agent technical field of nano material.
Background technology
Emulsion polymerization technology is sprouted last century early stage, realizes suitability for industrialized production the thirties.At present, letex polymerization has become the key areas of polymer science and technology, is one of important method of producing superpolymer." white glue with vinyl " is that vinyl acetate gets by letex polymerization, and be nontoxic because of easy to use, free from environmental pollution, and price cheaply is widely used in the industries such as building, furniture, paper product, leather binding agent.Its main drawback is that water tolerance, thermotolerance, winter hardiness are relatively poor, and cohesive strength is not high simultaneously, a little less than creep resistance, and the less stable of emulsion.Usually roughly can be divided into two classes to the method for modifying of polyvinyl acetate (PVA), the first kind is physical modification, and Equations of The Second Kind is the chemical copolymerization modification.Be mainly to add a certain amount of additive, outside cross-linking agent etc. in emulsion for physical modification, carry out compositely with emulsion, form the net macromolecular structure after making emulsion film forming, thereby improve water tolerance, winter hardiness, creep resistance and the adhesive property etc. of glued membrane.Intermingling material commonly used has urea-formaldehyde resin, isocyanate resin, melamine resin etc., for improving the freeze-thaw-stability of PVAc emulsion, improves the initial bonding strength of PVAc emulsion simultaneously, and the colloid that uses simultaneously protection is mainly the polyvinyl alcohol of acetalation.The introducing of these materials makes and contains free formaldehyde in the PVAc emulsion, if formaldehyde content exceeds standard, can cause atmospheric pollution, serious harm people's health.
Summary of the invention
The present invention provide for the formaldehyde pollution problem that solves the aqueous polyvinyl acetate emulsion that exists in background technology a kind of with the modified Nano attapulgite as protective colloid, prepare the method for nano-attapulgite stone modified polyvinyl acetate/α-pinene copolymer emulsion.
Technical scheme of the present invention is at first attapulgite to be activated and dispersion treatment; prepare the nano-attapulgite stone dispersion liquid; then adopt chelate surfactant to carry out surface modification as protective colloid and the emulsifying agent of letex polymerization to nano-attapulgite stone, prepare polyvinyl acetate (PVA)/α-pinene copolymer emulsion with it at last.
Step of the present invention is as follows:
1, the preparation of modified Nano attapulgite dispersion liquid:
Natural attapulgite is pulverized with the high energy nanon ball-mill milled, then after 2mol/L～3mol/L acid effect is processed, 25～85 ℃ of lower water-bath ultrasonic oscillation 1～6 h, centrifugal, wash to silver nitrate solution and detect without till precipitation, oven dry pulverizes and sieves.The acid that acidifying is adopted can be hydrochloric acid, sulfuric acid etc.The quality of attapulgite and acid solution is 0.05:1～0.5:1.to soak 5～10 days under the attapulgite normal temperature after processing, mechanical stirring or ultra-sonic dispersion were processed 1～4 hour, make the nano-attapulgite stone dispersion liquid, stir on one side, add N-oleic acid ethylenediamine triacetic acid sodium on one side in the nano-attapulgite stone dispersion liquid of gained, wherein N-oleic acid ethylenediamine triacetic acid sodium and nano-attapulgite stone mass ratio are (0.03～0.20): 1, be warming up to 65～85 ℃, reacted 5～10 hours, then adding volumetric molar concentration is that 0.3～0.2 mol/L sodium hydrogen carbonate solution to system pH value is 7.5～9.0, be warming up to 90～100 ℃, stirred 1～4 hour, filter, add deionized water dissolving, be mixed with the quality percentage composition and be 1%～10% modified Nano attapulgite dispersion liquid.
2, the preparation of polyvinyl acetate (PVA)/α-pinene copolymer emulsion:
Get step 1 gained modification dispersion liquid, add α-pinene and vinyl acetate mixing solutions, be warming up to 65～85 ℃, stirred 30～50 minutes, flow velocity take 10～20 ml/min adds mass percentage concentration as 1%～5% initiator solution, dropwises rear insulation reaction 60～90 minutes, is that 5%～15% basic solution regulation system pH value is 5.0～6.5 with mass percentage concentration, be cooled to the room temperature discharging, namely obtain nano-attapulgite stone/polyvinyl acetate composite emulsion.
Wherein said initiator solution is ammonium persulphate or potassium persulfate solution, described basic solution is a kind of in sodium hydrogen carbonate solution, sodium acetate soln and Sodium phosphate dibasic, described modified attapulgite and vinyl acetate mass ratio are (0.05～0.30): 1, α-pinene and Vinyl Acetate Monomer mass ratio are (0.01～0.05): 1, and initiator and vinyl acetate mass ratio are (0.005～0.015): 1.
The invention has the advantages that:
1, the present invention replaces aqueous polyvinyl acetate emulsion to prepare hydroaropic substance polyvinyl formal commonly used in title as protective colloid with the modified Nano attapulgite; thereby reduced the formaldehyde pollution of polyvinyl acetate composite emulsion, improved simultaneously its paint film water tolerance.
2, the present invention uses N-oleic acid ethylenediamine triacetic acid sodium to carry out surface modification to nano-attapulgite stone, process like this and mainly contain two aspect benefits: the one, make not only hydrophilic but also oleophylic of modified Nano attapulgite, has simultaneously the good emulsifying effect, do not need additionally to add emulsifying agent, and the ability of nano-attapulgite protective colloid is better under the chelate surfactant effect; The 2nd, the N-oleic acid ethylenediamine triacetic acid sodium of the two keys of band can with two kinds of monomer generation copolymerization; nano-attapulgite stone and the polyvinyl acetate (PVA) form with chemical bond is combined; strengthened the interaction force between protective layer and polymer particle; improved the stability of aqueous polyvinyl acetate emulsion; be difficult for producing precipitated and separated, improved mechanical property and the freeze-thaw resistance property of polyvinyl acetate composite emulsion.
3, the nano-attapulgite stone selected of the present invention has special one dimension fibre shape structure and more superior reinforcing property, further improved the cohesive strength of polyvinyl acetate composite emulsion, expanded its range of application, the selected nano-attapulgite stone of the present invention has simultaneously also played the effect of filler, need not to add other fillers.
4, the solid content of the polyvinyl acetate copolymerization emulsion that obtains of the present invention is usually below 30%, the white glue with vinyl emulsion that obtains lower than general method, to certain help that reduces production costs, do not introduce in process of production formaldehyde fully simultaneously, can not cause the environmental pollution in use procedure.Itself has bacteriostasis α-pinene, does not need to add extra biostats.
Embodiment
Below in conjunction with embodiment and Comparative Examples, the invention will be further described, but never limit the scope of the invention:
Embodiment 1
1,10 kilograms of attapulgites are joined in the hydrochloric acid soln that the double centner hydrogen ion concentration is 1 mol/L, soaked 10 days under normal temperature, mechanical stirring 4 hours, make the nano-attapulgite stone dispersion liquid, stir on one side, add 0.30 kilogram of N-oleic acid ethylenediamine triacetic acid sodium on one side in the nano-attapulgite stone dispersion liquid of gained, be warming up to 65 ℃, reacted 10 hours, then adding concentration is that sodium hydrogen carbonate solution to the system pH value of 2.0mol/L is 8.0, be warming up to 90 ℃, stirred 4 hours, filter and make the modified Nano attapulgite;
2, add deionized water in the filter cake of step 1 gained, stir, be mixed with the quality percentage composition and be 2% modified Nano attapulgite dispersion liquid, get 75 kilograms of this dispersion liquids, add 19.5 kilograms of vinyl acetates, 0.5 kilogram of α-pinene, be warming up to 65 ℃, stirred 50 minutes, add mass percentage concentration as 5 kilograms of 5% ammonium persulfate solutions take 20 ml/min flow velocitys, dropwise rear insulation 90 minutes, be that 15% sodium dihydrogen phosphate regulation system pH value is 5.0 with mass percentage concentration, be cooled to the room temperature discharging, namely make nano-attapulgite stone modified polyvinyl acetate/α-pinene copolymer emulsion.
Embodiment 2
1,6 kilograms of attapulgites being joined 20 kilograms of hydrogen ion concentrations is in the sulphuric acid soln of 1.0mol/L, soaked 20 days under normal temperature, ultra-sonic dispersion 1 hour, make the nano-attapulgite stone dispersion liquid, stir on one side, add 1.20 kilograms of N-oleic acid ethylenediamine triacetic acid sodium on one side in the nano-attapulgite stone dispersion liquid of gained, be warming up to 85 ℃, reacted 5 hours, then adding concentration is that sodium hydrogen carbonate solution to the system pH value of 0.3mol/L is 7.5, heat up 100 ℃, stirred 1 hour, filter and make the modified Nano attapulgite;
2, add deionized water in the filter cake of step 1 gained, stir, be mixed with the quality percentage composition and be 8% modified Nano attapulgite dispersion liquid, get 75 kilograms of this dispersion liquids, add 15 kilograms of vinyl acetates, 0.5 kilogram of α-pinene, be warming up to 85 ℃, stirred 30 minutes, add mass concentration as 20 kilograms of 1% ammonium persulfate solutions take 10 ml/min flow velocitys, dropwise rear insulation reaction 60 minutes, be that 5% sodium acetate soln regulation system pH value is 6.5 with mass percentage concentration, be cooled to the room temperature discharging, namely make nano-attapulgite stone/polyvinyl acetate composite emulsion.
Embodiment 3
1,10 kilograms of attapulgites being joined 50 kg of hydrogen ionic concns is in the sulphuric acid soln of 1.0mol/L, soaked 15 days under normal temperature, mechanical stirring 2 hours, make the nano-attapulgite stone dispersion liquid, stir on one side, add 1 kilogram of N-oleic acid ethylenediamine triacetic acid sodium on one side in the nano-attapulgite stone dispersion liquid of gained, be warming up to 75 ℃, reacted 8 hours, then add concentration be 1.0mol/L sodium hydrogen carbonate solution to system PH be 8.0, be warming up to 95 ℃, stirred 2 hours, filter and make the modified Nano attapulgite;
2, add deionized water in the filter cake of step 1 gained, stir, be mixed with the quality percentage composition and be 4% modified Nano attapulgite dispersion liquid, get 75 kilograms of this dispersion liquids, add 30 kilograms of vinyl acetates, 0.5 kilogram of α-pinene, be warming up to 75 ℃, stirred 40 minutes, add mass percentage concentration as 12 kilograms of 2.5% ammonium persulfate solutions take 15 ml/min flow velocitys, dropwise rear insulation reaction 75 minutes, be that 10% sodium hydrogen carbonate solution regulation system pH value is 6.0 with mass percentage concentration, be cooled to the room temperature discharging, namely make nano-attapulgite stone/polyvinyl acetate composite emulsion.
Comparative Examples 1: in Comparative Examples 1, as protective colloid, concrete operations are as follows with polyvinyl formal:
Add 3 kilograms of polyvinyl formals in 72 kilograms of deionized waters, stir fully dissolving, add 30 kilograms of vinyl acetates, be warming up to 75 ℃, stirred 40 minutes, add mass percentage concentration as 12 kilograms of 2.5% ammonium persulfate solutions take 15 ml/min flow velocitys, dropwise rear insulation reaction 75 minutes, with mass percentage concentration be 10% sodium hydrogen carbonate solution to regulate pH value be 6.0, be cooled to the room temperature discharging, namely make aqueous polyvinyl acetate emulsion.
Nano-attapulgite stone/polyvinyl acetate composite emulsion performance evaluation
Below by performance test, polyvinyl acetate composite emulsion and the nano-attapulgite stone/polyvinyl acetate composite emulsion of testing gained carried out performance evaluation, experimental result is as shown in table 1.
Bonding strength test: bonding strength press the method test described in GB/T 14074-1993, and adopting pine is that material was colded pressing 2 days, and then AGS-J type tension testing machine (Japanese Shimadzu company) is tested.Then its test specimen is immersed in 60 ℃ of water 3 hours, immediately test specimen is lain in (23 ± 2) ℃ air convection drying case dry 10 hours, then survey its bonding strength.
As can be seen from Table 1, the present invention prepared nano-attapulgite stone/the polyvinyl acetate composite emulsion water resistance is significantly improved, and stability is better.
Table 1 nano-attapulgite stone/polyvinyl acetate composite emulsion performance test
| ? | Bonding strength (MPa) | Bonding strength (MPa) after dipping | Stability |
| Embodiment 1 | 12.8 | 7.2 | 1 year not stratified |
| Embodiment 2 | 11.5 | 7.1 | 1 year not stratified |
| Embodiment 3 | 12.0 | 8.5 | 1 year not stratified |
| Comparative Examples 1 | 4.0 | Split | Layering in two days |
Claims (2)
1. preparing polyvinyl acetate/alpha-pinene copolymer emulsion through modification of nano-attapulgite synthetic method, it is characterized by concrete steps as follows: the preparation of the dispersion liquid of (1) nano-attapulgite stone: attapulgite is pulverized by the high energy nanon ball-mill milled, obtain the nano level attapulgite, the nano-attapulgite stone that obtains is entered in the hydrochloric acid or sulphuric acid soln of hydrogen ion volumetric molar concentration 2 ~ 3 mol/L, wherein attapulgite and hydrochloric acid or sulphuric acid soln mass ratio are 0.05 ~ 0.5:1, soaked under normal temperature 5 ~ 10 days, mechanical stirring or ultra-sonic dispersion were processed 2 ~ 5 hours, stir on one side, add N-oleic acid ethylenediamine triacetic acid sodium on one side in the nano-attapulgite stone dispersion liquid of gained, N-oleic acid ethylenediamine triacetic acid sodium and nano-attapulgite stone mass ratio are (0.03～0.20): 1, then adding volumetric molar concentration is that 0.3～0.2 mol/L sodium hydrogen carbonate solution to system pH is 7.5～9.0, be warming up to 90～100 ℃, stirred 1～4 hour, filter, add deionized water dissolving, be mixed with the quality percentage composition and be 1%～10% modified Nano attapulgite dispersion liquid, (2) preparation of polyvinyl acetate (PVA)/α-pinene copolymer emulsion: get step 1 gained modification dispersion liquid, add α-pinene and vinyl acetate mixing solutions, be warming up to 65～85 ℃, stirred 30～50 minutes, flow velocity take 10～20 ml/min adds mass percentage concentration as 1%～5% initiator solution, dropwise rear insulation reaction 60～90 minutes, be that 5%～15% basic solution regulation system pH value is 5.0～6.5 with mass percentage concentration, be cooled to the room temperature discharging, namely obtain nano-attapulgite stone/polyvinyl acetate composite emulsion.
According to claim 1 in wherein said a kind of preparing polyvinyl acetate/alpha-pinene copolymer emulsion through modification of nano-attapulgite synthetic method, it is characterized in that: described initiator solution is ammonium persulphate or potassium persulfate solution; Described basic solution is a kind of in sodium hydrogen carbonate solution, sodium acetate soln or Sodium phosphate dibasic.
3Wherein said a kind of preparing polyvinyl acetate/alpha-pinene copolymer emulsion through modification of nano-attapulgite synthetic method according to claim 1, it is characterized in that: described modified attapulgite and vinyl acetate mass ratio are (0.05～0.30): 1, α-pinene and Vinyl Acetate Monomer mass ratio are (0.01～0.05): 1, and initiator and vinyl acetate mass ratio are (0.005～0.015): 1.
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