CN101817904B - Method for producing vinyl acetate multi-copolymerization emulsion - Google Patents
Method for producing vinyl acetate multi-copolymerization emulsion Download PDFInfo
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- CN101817904B CN101817904B CN2010101603879A CN201010160387A CN101817904B CN 101817904 B CN101817904 B CN 101817904B CN 2010101603879 A CN2010101603879 A CN 2010101603879A CN 201010160387 A CN201010160387 A CN 201010160387A CN 101817904 B CN101817904 B CN 101817904B
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Abstract
The invention discloses a method for producing vinyl acetate multi-copolymerization emulsion, which comprises the following steps of: a, polymerizing seeds; b, polymerizing core segments; c, polymerizing shell segments; and d, preserving heat. The invention aims to overcome the defects in the prior art, and provides a method for producing vinyl acetate multi-copolymerization emulsion which has the advantages of high solid content, less residual monomers and small smell.
Description
Technical field
The present invention relates to a kind of method of producing vinyl acetate multi-copolymerization emulsion.
Background technology
The polymerization property of vinyl-acetic ester is: when carrying out Raolical polymerizable, compare with other vinyl monomer; The activity of vinyl acetate monomer and Raolical polymerizable relatively weak (Li Keyou, Zhang Juhua, Xiang Furu etc.; Polymer Synthesizing principle and technic; Science Press, P232 in 1999).Therefore, when vinyl-acetic ester carried out homopolymerization or copolymerization, small amounts of monomer was residual easily.
Zhang Yulong writes, " adhesive formulation is selected ", Chemical Industry Press; In January, 2004 first version, vinyl acetate-tertiary ethylene carbonate in 136 examples-Bing Xisuandingzhi copolymer emulsion, holding stage add tertbutyl peroxide, sodium formaldehyde sulfoxylate (rongalite) oxidation-reduction initiator remains in the product to reduce monomers such as free acetic acid vinyl acetate; This method is feasible; But often ignored the vinyl-acetic ester characteristic in the polymerization process, thereby it is remaining to have more vinyl-acetic ester, takes measures to make the vinyl-acetic ester reaction more complete at holding-zone; Often be difficult to the result that reaches satisfied, still have the residual monomer smell.
The residual monomer of product is higher, can bring environmental pollution in the application.After being incubated, vacuumize, make monomer reductions such as residual vinyl-acetic ester, not only influence solid content, equally human body and living environment are brought direct harm.Because of most of volatile organic compounds all can be participated in photochemical reaction, generate ozone, global environment is also brought destruction.Therefore, reduce monomer content such as residual vinyl-acetic ester, have feasibility, urgency.
Summary of the invention
The objective of the invention is provides a kind of solid content than higher, the working method of the vinyl acetate multi-copolymerization emulsion that residual monomer is low, smell is minimum in order to overcome weak point of the prior art.
In order to achieve the above object, the present invention adopts following scheme:
A kind of method of producing vinyl acetate multi-copolymerization emulsion may further comprise the steps:
A, " seed " polymerization
With the water component; The Z 150PH of steady dissolution agent in advance, polyvinyl formal solution, anionic emulsifier, buffer reagent and bottoming water are gone into still, start stirring, then 1/7～1/10 vinyl acetate monomer are gone into still emulsification; Slowly be warmed up to 50～60 ℃ of addings " seed " initiator solution; Treat that orchid occurs mutually, temperature is raised to 80～82 ℃, does not reflux until having;
B, " nuclear section " polymerization
Adopt 6～10 gradation to drip vinyl-acetic ester, tertiary ethylene carbonate, contain the mixed solution of carboxylic monomer and other function monomers, drip the dropping respectively synchronously of mix monomer and initiator solution at every turn, dropping temperature remains on 75～80 ℃; After dripping, treat that monomer polymerization is complete, temperature is raised to 80～82 ℃ at every turn; Then carrying out the metering second time drips; Add as last time operating, totally 2.5～3 hours, be incubated 30～40 minutes until " nuclear section " monomer;
C, " shell section " polymerization
Mix monomers such as (methyl) acrylic ester monomer, vinyl cyanide or Alpha-Methyl vinyl cyanide, mix monomer and initiator solution drip respectively synchronously continuously, until accomplishing " shell section " polymerization, need 1.5～2 hours;
D, insulation
Earlier will the component except that oxygenant process the aqueous solution and add a spare tape valve pipe from still hand hole or port lid and add the still, oxygenant then splashes into the still from the initiator scale tank, dropwises in 30～40 minutes; Continue insulation 1.5～2 hours, be cooled to about 50 ℃ after insulation finishes, add plasticizer components; Mixed 20～30 minutes; Cool to 40 ℃ afterwards, discharging, filtration, packing are product of the present invention.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, the wherein said carboxylic monomer that contains is methylacrylic acid, vinylformic acid, MALEIC ANHYDRIDE, methylene-succinic acid.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, wherein said initiator are the agent of oxidation-reduction primosome.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, the agent of wherein said oxidation-reduction primosome are persulphate-sulphite and organic polyamine combined oxidation-reduction initiator.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, wherein said persulphate is Potassium Persulphate or ammonium persulphate.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, wherein said sulphite are sodium sulfite anhy 96, formolation hydrosulphite or ammonium thiosulfate.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, wherein said organic polyamine are a kind of in diethylenetriamine to nine ethene ten amine.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, wherein said oxygenant: reductive agent (quality)=1～3: 3～6.
Aforesaid a kind of method of producing vinyl acetate multi-copolymerization emulsion, wherein said sulphite and organic polyamine mass ratio are 0.1～1: 0.5～3.0.
In sum, beneficial effect of the present invention:
Working method of the present invention is formulated than propenoate is low according to the vinyl-acetic ester initiating activity, and the product solid content that production obtains compares higher, and monomer residue is low, smell is minimum.Its solid content of product of comparing the present invention's production with existing same product is high by about 1%, and free monomer reduces by 1～2 times, and obnoxious flavour is overflowed and lacked in the product use, and is favourable to HUMAN HEALTH and environment protection.
Embodiment
Below in conjunction with embodiment the present invention is done and to further describe:
The poly-unit that the production vinyl acetate multi-copolymerization emulsion is used comprises monomer mixing storage tank 1 (volume 500 liters); Initiator configured slot 2 (volume 80 liters); " nuclear " section mix monomer scale tank 3 (volume 40 liters); Initiator scale tank 4 (volume 10 liters); Band scale glass bushing liquid level meter 5,6; Reflux exchanger 7 (6 square metres of heat transfer areas); Look clock 8; The arm 9 of band valve on the hand hole; Connect chuck fluid level control system 10; Polymerization reaction kettle 11 (volume 1000 liters); Outfall sewer 12.
Embodiment 1
Dissolve polyvinyl alcohol PVA1788 or PVA1792 are made into the aqueous solution and draw off subsequent use in polymerization reaction kettle 11.The same PVF solution that in polymerization reaction kettle 11, prepares 10% concentration of PVA1799 or 1792 is emitted subsequent use.Press formula ratio preparation " shell " section water component with polymerization reaction kettle 11; Water-phase component is deionized water, sodium lauryl sulphate (SDS), polyoxyethylene nonylphenol (NP-40 or OP-10), buffer reagent etc.; Heating about 40 ℃, stirring and dissolving is even, draws off subsequent use.Before the polymerization respectively in monomer mixing storage tank 1, prepare monomer mixed solution, the finite concentration ammonium persulfate initiator aqueous solution in the initiator Preparation tank 2; Get the raw materials ready and finish deionized water, 10% polyvinylformal liquid, 10%PVA-1792 or 10%PVA-1788 solution to be added the still from manhole or hand hole by prescription; Start and stir, add formula ratio buffer reagent NaHCO respectively from manhole or hand hole
3, sodium lauryl sulphate (SDS) and polyoxyethylene nonylphenol nonionic emulsifying agents such as (NP-40 or OP-10), cover manhole or hand hole.Slowly heat up, open the water inlet pipe valve of reflux condensation mode, the dissolving homogeneous adds seeding polymerization monomer vinyl-acetic ester simultaneously the spare tape valve arm from hand hole, carry out emulsification.Treat that temperature is raised to 50～60 ℃ of initiator solutions that add seed section aequum, continues to heat up, approximately to 72 ℃; Orchid occurs mutually, and this moment, monomer refluxed in a large number, until about 80 ℃; Basically do not have the backflow monomer,, see that looking clock 8 does not have backflow 80～82 ℃ of insulations 5～10 minutes; " seed " polymeric segment is accomplished, and gets into the polymerization of " nuclear " section.
The polymerization of " nuclear " section; Press 6 or 10 charging technologies at every turn from the monomer tempering tank; Quantitatively put into " nuclear " section mix monomer to " nuclear " section mix monomer scale tank 3; Nuclear " section monomer comprise vinyl-acetic ester, tertiary ethylene carbonate and contain the carbonyl monomer and function monomer such as vinylformic acid, methylacrylic acid, methylene-succinic acid or MALEIC ANHYDRIDE etc. that initiator is then put into initiator scale tank 4 from initiator Preparation tank 2.Both drip synchronously.If 10 times drip, drip 12～15 minutes time at every turn.If, dripped 20～25 minutes at every turn by twice.Temperature is controlled at 74～78 ℃ during the dropping, dropwises at every turn, carries out temperature with reaction and raises; 80～82 ℃ of may command do not reflux until having, and generally need 3～5 minutes can reach the nothing backflow approximately; Can enter into the operation next time this moment; Press with the CONTROL PROCESS first time, feeding in raw material until " nuclear " section finishes, and " nuclear " section feeding study on period was generally about 3 hours.After " nuclear " section has been fed in raw material, be incubated 30 minutes.
In " nuclear " when insulation section; Promptly in monomer mixing storage tank 1, prepare " shell " section monomer; " shell " section monomer is TEB 3K, Bing Xisuandingzhi, vinyl cyanide, Alpha-Methyl vinyl cyanide, contains carboxylic monomer and function monomer, cofabrication " shell " section initiator ammonium persulfate aqueous solution.After insulation finishes, from hand hole standby pipes is installed and adds " shell " section water-phase component.Treat that temperature is raised to about 80 ℃, drip " shell " section mix monomer, initiator solution synchronously.80～84 ℃ of control dropping temperatures need about 150 minutes altogether.
After the polymerization of " shell " section is accomplished, get into soak.Preceding 30～50 minutes adding oxidation-reduction initiators in insulation.Impel remaining monomer polymerization.Present embodiment meets initiator system with persulphate-sulphite and organic polyamine oxidation-reduction.Persulphate can be used Potassium Persulphate, ammonium persulphate etc.Sulphite can be used sodium sulfite anhy 96, formolation hydrosulphite, Sulfothiorine etc.Best with rongalite or sodium sulfite anhy 96.Organic polyamine can be with diethylenetriamine to nine ethene ten amine etc.Its polyamines is best with the effect of diethylenetriamine to five ethene hexamine.Its oxygenant: reductive agent (quality)=1～3: 3～6.In the reduction, sulphite and organic polyamine mass ratio are 0.1～1: 0.5～3.0.Present embodiment uses ammonium persulphate to make oxygenant, rongalite, diethylenetriamine to be complex reducing agent; 100 parts of weight monomers of every throwing; Select ammonium persulphate, rongalite, diethylenetriamine, its quality is respectively 0.05～0.15,0.01～0.3,0.06～0.2 part of quality for well.Be made into the aqueous solution respectively, also the ancestral home can once add, and oxygenant then adopts dropping technology.Insulation finishes, and is cooled to about 50 ℃, adds softening agent and stirs 20～30 minutes, cooling discharge, filtration, packing.Extremely low by this law sintetics levels of residual monomers, residual village monomer mass percentage ratio is 0.52%, and smell is few.
Comparative Examples 1
Prescription and technology just get into " nuclear " section and drip " nuclear " section mix monomer and initiator solution, about 150 minutes of time continuously after only " seed " polymerization orchid occurs mutually with embodiment 1 basically.The insulation of " nuclear " section was kept 30 minutes still at 80～84 ℃, behind supplement formula amount " shell " the section emulsifier aqueous solution, got into the polymerization of " shell " section, still was continuous charging, and the time is identical with embodiment 1.The reinforced end is incubated, adds initiator potassium persulfate or ammonium persulphate, and 100 parts of weight unit of its amount add 0.1～0.4 part, with 0.2 part for well.Being made into the aqueous solution dripped off in preceding 30 minutes that are incubated.Cool at last about 50 ℃, add softening agent and stirred cooling discharge, filtration, packing 20～30 minutes.Comparative Examples 1 free monomer amount is big, and remaining vinyl acetate monomer massfraction is 1.12%, and sharp aroma is arranged.
Comparative Examples 2
Prescription and technology are basically with embodiment 1, and only orchid presents just continuous " nuclear " section mix monomer, the initiator solution of dripping in back mutually, lasts about 150 minutes; Dropwise, be incubated 30 minutes, add emulsifier aqueous solution; Treat that temperature is raised to 80～82 ℃; Drip continuously " shell " section mix monomer, initiator solution dropwises and is incubated.
Superoxide-ferrous oxidation-reduction system initiator is added in insulation.Comparative Examples 2 used oxidation-reduction trigger systems are ammonium persulphate, ferrous sulfate, rongalite and EDTA, and its amount is respectively 0.06～0.2,0.01～0.5,0.04～0.3,0.01～0.05 part of quality by 100 parts of quality monomer that feeds intake.Ammonium persulphate, ferrous sulfate, rongalite, the preferable amount of EDTA are 0.08～0.15,0.02～0.04,0.05～0.2,0.02～0.03 part.The free monomer amount is lower, and monomer mass marks such as its remaining vinyl-acetic ester are 2.84%, and smell is less.
Embodiment 1 and Comparative Examples 1, Comparative Examples 2 are produced among the present invention product performance and the key technical indexes, see the following form:
Its solid content of product that the inventive method is produced is about 52%, and give birth suddenly product scale by 2000 every year, and monomers such as vinyl-acetic ester are on average pressed 12000 yuan/, escapable cost 170,000 to 250,000.And the product that the inventive method is produced is easy to sell, quality product improves, and is little to the HUMAN HEALTH infringement, is beneficial to environment protection.
Claims (8)
1. method of producing vinyl acetate multi-copolymerization emulsion is characterized in that may further comprise the steps:
A, " seed " polymerization
With the water component; The Z 150PH of steady dissolution agent in advance, polyvinyl formal solution, anionic emulsifier, buffer reagent and bottoming water are gone into still, start stirring, then 1/7～1/10 vinyl acetate monomer are gone into still emulsification; Slowly be warmed up to 50～60 ℃ of addings " seed " initiator solution; Treat that orchid occurs mutually, temperature is raised to 80～82 ℃, does not reflux until having;
B, " nuclear section " polymerization
Adopt 6～10 gradation to drip vinyl-acetic ester, tertiary ethylene carbonate, contain the mixed solution of carboxylic monomer and other function monomers, drip the dropping respectively synchronously of mix monomer and initiator solution at every turn, dropping temperature remains on 75～80 ℃; After dripping, treat that monomer polymerization is complete, temperature is raised to 80～82 ℃ at every turn; Then carrying out the metering second time drips; Add as last time operating, totally 2.5～3 hours, be incubated 30～40 minutes until " nuclear section " monomer; Wherein said other function monomers are vinylformic acid, methylacrylic acid, methylene-succinic acid or MALEIC ANHYDRIDE;
C, " shell section " polymerization
(methyl) acrylic ester monomer, vinyl cyanide or Alpha-Methyl vinyl cyanide mix monomer, mix monomer and initiator solution drip respectively synchronously continuously, until accomplishing " shell section " polymerization, need 1.5～2 hours;
D, insulation
Earlier will the component except that oxygenant process the aqueous solution and add a spare tape valve pipe from still hand hole or port lid and add the still, oxygenant then splashes into the still from the initiator scale tank, dropwises in 30～40 minutes; Continue insulation 1.5～2 hours, be cooled to about 50 ℃ after insulation finishes, add plasticizer components; Mixed 20～30 minutes; Cool to 40 ℃ afterwards, discharging, filtration, packing are vinyl acetate multi-copolymerization emulsion.
2. a kind of method of producing vinyl acetate multi-copolymerization emulsion according to claim 1 is characterized in that the described carboxylic monomer that contains is methylacrylic acid, vinylformic acid, MALEIC ANHYDRIDE, methylene-succinic acid.
3. a kind of method of producing vinyl acetate multi-copolymerization emulsion according to claim 1 is characterized in that described initiator is the agent of oxidation-reduction primosome.
4. a kind of method of producing vinyl acetate multi-copolymerization emulsion according to claim 3 is characterized in that the agent of described oxidation-reduction primosome is persulphate-sulphite and organic polyamine combined oxidation-reduction initiator.
5. a kind of method of producing vinyl acetate multi-copolymerization emulsion according to claim 4 is characterized in that described persulphate is Potassium Persulphate or ammonium persulphate.
6. a kind of method of producing vinyl acetate multi-copolymerization emulsion according to claim 4 is characterized in that described sulphite is sodium sulfite anhy 96, formolation hydrosulphite or ammonium thiosulfate.
7. a kind of method of producing vinyl acetate multi-copolymerization emulsion according to claim 4 is characterized in that described oxygenant: reductive agent (quality)=1～3: 3～6.
8. a kind of method of producing vinyl acetate multi-copolymerization emulsion according to claim 4 is characterized in that described sulphite and organic polyamine mass ratio are 0.1～1: 0.5～3.0.
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| CN105482021B (en) * | 2016-01-19 | 2018-08-28 | 广东衡光新材料科技有限公司 | The preparation of the vac-veova emulsion of excellent combination property and related coating |
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