CN105237671A - Terpolymer emulsion containing 1-vinyl imidazole, and preparation method thereof - Google Patents
Terpolymer emulsion containing 1-vinyl imidazole, and preparation method thereof Download PDFInfo
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- CN105237671A CN105237671A CN201510644598.2A CN201510644598A CN105237671A CN 105237671 A CN105237671 A CN 105237671A CN 201510644598 A CN201510644598 A CN 201510644598A CN 105237671 A CN105237671 A CN 105237671A
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- vinyl imidazole
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Abstract
The invention discloses a terpolymer emulsion containing 1-vinyl imidazole. The emulsion comprises, by mass, 40-60% of vinyl chloride, 10-25% of vinyl acetate, 1-10% of 1-vinyl imidazole, 2-5% of a nonionic emulsifier, 1-5% of diethylenetriamine, 0.1-2% of hydroquinone, 0.1-3% of ammonium persulfate and 5-15% of deionized water. The terpolymer emulsion containing 1-vinyl imidazole has the advantages of excellent stability, high density of a paint film, small particle size, and good water, acid and alkali resistance; and a vinyl chloride, vinyl acetate and 1-vinyl imidazole monomer copolymerization technology adopted in the invention has the advantages of simplicity, easy operation, easy control of the reaction speed, low cost, and environment protection principle meeting. The invention also discloses a preparation method of the terpolymer emulsion containing 1-vinyl imidazole.
Description
Technical field
The invention belongs to coating and preparing technical field thereof, be specifically related to a kind of copolymer emulsion containing 1-vinyl imidazole and preparation method thereof.The present invention is applied particularly to metallic substance corrosion-resistant field.
Background technology
Polyvinyl chloride has the advantages such as good mechanical property, fire-retardant, the rotten candle of chemically-resistant, is widely used in the fields such as building materials, electric wire, agricultural film, imitation leather.But, polyvinyl chloride in low polar solvent poorly soluble, coating adhesion is not strong; Meanwhile, supervinyi chloride resin heat is easily decomposed, and has started slow decomposition at 80 ~ 90 DEG C, causes paint film color to deepen after decomposition, degraded toughness, becomes fragile, and erosion resistance reduces.Therefore normal employing and the method for other monomer copolymerization, to obtain the copolymer resins of different performance, expand its Application Areas.Chlorovinyl-acetate vinyl copolymer resins is most important one in vinyl chloride copolymer resins, produced by U.S. combinating carbide company the earliest, external main manufacturer has German Wa Ke company, Japanese Xin company, Belgian Solvey company etc. now, and domestic main manufacturer has Jiangsu Hong Hui resin company limited, Xinfeng, Anhui Chemical Co., Ltd., Xinjiang Zhong Fa Chemical Co., Ltd. etc.Compare with polyvinyl chloride, vinyl acetate ester structure is introduced in Chlorovinyl-acetate vinyl copolymer resins molecule, in reservation polyvinyl chloride chemically-resistant corruption candle, the performance basis such as fire-retardant, copolymer emulsion is also made easily to process, solvability is also improved greatly, be dissolvable in water the low polar solvents such as butanone, and improve the sticking power of copolymer emulsion to various base material.Therefore, Chlorovinyl-acetate vinyl copolymer resins is one of desirable adhesion component raw material, can be applicable to the fields such as ink, fire-proof and water-proof paint, automobile finish and steamer paint.
Along with the widespread use of environmental protection in coating and ink industry, low polar solvent, the solubility property of Chlorovinyl-acetate vinyl copolymer resins is had higher requirement.In order to improve the hardness of coating, and improving the cohesive force with the base material such as metal, the also normal Third monomer introducing imidazole group in Chlorovinyl-acetate vinyl copolymer resins, be wherein the most frequently used is 1-vinyl imidazole.1-vinyl imidazole is used for the stiffening agent of resin material, and the nucleome of coating, resin inclusion, can strengthen the film forming ability of resin or coating, when better strengthening application and the binding ability of base material.Also may be used for petroleum industry and be used as high polymer, such as, with isoprene catalysis lithiation technique, the remover of vinyl protecting group.
At present, the copolymer resins of state's inside courtyard, ink is mainly raw material with vinyl chloride-vinyl acetate copolymer resin, itself and vinyl alcohol, ethene and toxilic acid etc. are carried out modification by copolymerization, prepares high performance ternary copolymer emulsion.Patent CN200710022759.X discloses a kind of preparation method of vinyl chloride-vinyl acetate-vinyl alcohol copolymer thing, prepare high performance vinyl chloride-vinyl acetate-vinyl alcohol copolymer thing emulsion, but it have employed the organic solvent such as acetone, MEK; Patent CN200810194879.2 discloses a kind of chloroethylene-vinyl acetate-maleic acid copolymerized thing and obtains preparation method, but, in process of production, only have the toxilic acid of 10% to participate in copolymerization, all the other 90% maleic acid copolymerizedly not go up.
At present, domestic except minority producer with micro-suspension polymerization produce Low vinyl acetate content Chlorovinyl-acetate vinyl copolymer resins except, also do not have producer to adopt emulsion copolymerization to produce coating and ink, Chlorovinyl-acetate vinyl copolymer resins that solvability is good, and the research of vinylchlorid-vinyl-acetic ester-1-vinyl imidazole ternary copolymer emulsion more lack.
Summary of the invention
The object of the invention is to solve prior art Problems existing and deficiency, a kind of copolymer emulsion containing 1-vinyl imidazole and preparation method thereof is provided.The present invention is suitable for being coated with the water-borne coatings being contained in metallic substrate surface, and coating has good sticking power, Corrosion Protection and good weathering resistance.
For achieving the above object, the present invention, by being incorporated in vinylchlorid-vinyl acetate polymer emulsion by 1-vinyl imidazole, not only increase the acid-proof alkaline of coating, sticking power and antiseptic property, and technique is simple, transformation efficiency reaches more than 50%, and meets environmental friendliness principle.The present invention realizes the concrete technical scheme that object adopts:
A copolymer emulsion containing 1-vinyl imidazole, by mass percentage, each material of composition and content thereof are:
Wherein, the molecular structural formula that described terpolymer comprises is following formula:
Described nonionic emulsifying agent is containing, for example lower molecular structural formula:
A=5 ~ 20; R to be carbonatoms be 1 ~ 18 alkyl or
The preparation feedback equation of described nonionic emulsifying agent is as follows:
Wherein, a=5 ~ 20; R to be carbonatoms the be alkyl of 1 ~ 18,
In order to achieve the above object, the present invention solves another technical scheme that its technical problem adopts and is:
A preparation method for copolymer emulsion containing 1-vinyl imidazole, comprises the steps:
(1) add in reactor deionized water, vinyl-acetic ester, diethylenetriamine, the nonionic emulsifying agent of 50%, the ammonium persulphate of 50% and 50% vinylchlorid, rapid temperature increases to 65 DEG C ~ 100 DEG C, simultaneously, constantly stir with the stirring velocity of 1000 ~ 1500r/min, insulation reaction 4 ~ 15h, obtains vinylchlorid-acrylic ester emulsion;
(2) temperature of reactor is controlled at 65 DEG C ~ 100 DEG C, with the stirring velocity of 1000 ~ 1500r/min, add wherein successively while stirring the vinylchlorid of residue 50%, the ammonium persulphate of 50% and 50% nonionic emulsifying agent, and slowly drip 1-vinyl imidazole, be incubated 4 ~ 15h after dropwising, add Resorcinol;
(3) by products therefrom through 800 order filter screen filtration, obtain the copolymer emulsion containing 1-vinyl imidazole.
The advantage that the present invention is had compared with prior art and beneficial effect:
1-vinyl imidazole and vinylchlorid-vinyl-acetic ester are carried out letex polymerization by the proposition of novelty of the present invention, obtain vinylchlorid-vinyl-acetic ester-1-vinyl imidazole ternary copolymer emulsion, prepared ternary copolymer emulsion is compared to vinylchlorid-vinyl acetate copolymerization emulsion, stability significantly improves, the water tolerance of film improves, the hardness of coating becomes large, and also significantly strengthens with the cohesive force of the base material such as metal.Emulsion and microsuspension can adopt interval, the operating method advantage such as semicontinuous and continuous adopts water as medium, and Environmental Safety, is convenient to heat transfer and continuous prodution, and product all comparative superiority in solvability, molecular weight distribution and adhesive property.Adopt emulsion polymerisation process to produce vinylchlorid-vinyl-acetic ester-1-vinyl imidazole ternary copolymer emulsion, operating method is various, on copolymer emulsion composition control compared to additive method advantageously.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below enumerating embodiment and the present invention is described in further detail.It will be appreciated by those skilled in the art that described embodiment only understands the present invention for helping, being not intended to limit the present invention.
Embodiment 1
One, component content proportioning by mass percentage:
Two, preparation method:
(1) add in reactor deionized water, vinyl-acetic ester, diethylenetriamine, the nonionic emulsifying agent of 50%, the ammonium persulphate of 50% and 50% vinylchlorid, rapid temperature increases to 65 DEG C ~ 100 DEG C, simultaneously, constantly stir with the stirring velocity of 1000 ~ 1500r/min, insulation reaction 4 ~ 15h, obtains vinylchlorid-vinyl acetate emulsion;
(2) temperature of reactor is controlled at 65 DEG C ~ 100 DEG C, with the stirring velocity of 1000 ~ 1500r/min, add wherein successively while stirring the vinylchlorid of residue 50%, the ammonium persulphate of 50% and 50% nonionic emulsifying agent, and slowly drip 1-vinyl imidazole, be incubated 4 ~ 15h after dropwising, add Resorcinol;
(3) by products therefrom through 800 order filter screen filtration, obtain the copolymer emulsion containing 1-vinyl imidazole.
Three, the beneficial effect of the present embodiment:
The median size being recorded the emulsion particle concentration of polymer emulsion by nano-particle size analysis instrument is about 35nm; Actual measurement solids content 27.6%; Water tolerance is that 70h does not whiten, non-foaming.
Embodiment 2
One, component content proportioning by mass percentage
Two, preparation method is identical with embodiment 1.
Three, the beneficial effect of the present embodiment:
The median size being recorded the emulsion particle concentration of polymer emulsion by nano-particle size analysis instrument is that 6.7nm is left
Right; Actual measurement solids content 21.4%; Water tolerance is that 72h does not whiten, non-foaming.
Embodiment 3
One, component content proportioning by mass percentage:
Two, preparation method is identical with embodiment 1.
Three, the beneficial effect of the present embodiment:
The median size being recorded the emulsion particle concentration of polymer emulsion by nano-particle size analysis instrument is about 3.5nm; Actual measurement solids content 25.4%; Water tolerance is that 72h does not whiten, non-foaming.
Embodiment 4
One, component content proportioning by mass percentage
Two, preparation method is identical with embodiment 1.
Three, the beneficial effect of the present embodiment:
The median size being recorded the emulsion particle concentration of polymer emulsion by nano-particle size analysis instrument is about 6.3nm; Actual measurement solids content 21.9%; Water tolerance is that 68h does not whiten, non-foaming.
Embodiment 5
One, component content proportioning by mass percentage
Two, preparation method is identical with embodiment 1.
Three, the beneficial effect of the present embodiment:
The median size being recorded the emulsion particle concentration of polymer emulsion by nano-particle size analysis instrument is about 7.4nm; Actual measurement solids content 24.9%; Water tolerance is that 62h does not whiten, non-foaming.
Embodiment 6
One, component content proportioning by mass percentage:
Two, preparation method is identical with embodiment 1.
Three, the beneficial effect of the present embodiment:
The median size being recorded the emulsion particle concentration of polymer emulsion by nano-particle size analysis instrument is about 8.8nm; Actual measurement solids content 32%; Water tolerance is that 55h does not whiten, non-foaming.
The above, be only the present invention's preferably specific embodiment.Certainly; the present invention also can have other various embodiments, when not deviating from the present invention's spirit and essence thereof, is anyly familiar with those skilled in the art; change and distortion when various corresponding equivalence can be made according to the present invention, all should belong to the protection domain of the claim appended by the present invention.
Claims (4)
1. the copolymer emulsion containing 1-vinyl imidazole, is characterized in that: each material that described emulsion comprises and mass percentage content thereof are:
Wherein, the molecular structural formula that described terpolymer comprises is:
In formula: n=10 ~ 500, m=3 ~ 200, k=3 ~ 200.
2. a kind of copolymer emulsion containing 1-vinyl imidazole according to claim 1, is characterized in that: described nonionic emulsifying agent is containing, for example lower molecular structural formula:
A=5 ~ 20; R to be carbonatoms be 1 ~ 18 alkyl or
3. a kind of copolymer emulsion containing 1-vinyl imidazole according to claim 1 and 2, is characterized in that: the preparation feedback equation of described nonionic emulsifying agent is as follows:
A=5 ~ 20; R to be carbonatoms the be alkyl of 1 ~ 18,
4. a preparation method for a kind of copolymer emulsion containing 1-vinyl imidazole according to claim 1, is characterized in that: comprise the steps:
(1) add in reactor deionized water, vinyl-acetic ester, diethylenetriamine, the nonionic emulsifying agent of 50%, the ammonium persulphate of 50% and 50% vinylchlorid, rapid temperature increases to 65 DEG C ~ 100 DEG C, stir with the stirring velocity of 1000 ~ 1500r/min, insulation reaction 4 ~ 15h, obtains vinylchlorid-vinyl acetate emulsion;
(2) temperature of reactor is controlled at 65 DEG C ~ 100 DEG C, with the stirring velocity of 1000 ~ 1500r/min, add wherein successively while stirring the vinylchlorid of residue 50%, the ammonium persulphate of 50% and 50% nonionic emulsifying agent, and slowly drip 1-vinyl imidazole, continue after dropwising stir and be incubated 4 ~ 15h, add Resorcinol;
(3) by step (2) products therefrom through 800 order filter screen filtration, obtain the copolymer emulsion containing 1-vinyl imidazole.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510644598.2A CN105237671A (en) | 2015-10-08 | 2015-10-08 | Terpolymer emulsion containing 1-vinyl imidazole, and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510644598.2A CN105237671A (en) | 2015-10-08 | 2015-10-08 | Terpolymer emulsion containing 1-vinyl imidazole, and preparation method thereof |
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| CN105237671A true CN105237671A (en) | 2016-01-13 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111350A (en) * | 2015-08-28 | 2015-12-02 | 江苏科技大学 | Terpolymer emulsion containing 1-vinyl iminazole and preparation method thereof |
| CN105585907A (en) * | 2016-03-02 | 2016-05-18 | 无锡雅邦化学有限公司 | Corrosion-inhibition anticorrosive paint with chlorine-containing polymer emulsion |
| CN105969103A (en) * | 2016-07-12 | 2016-09-28 | 广州中海环保科技有限公司 | Vinyl chloride-vinyl acetate-vinyl ester ternary polymer water-based resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106961A (en) * | 1999-10-01 | 2001-04-17 | Tosoh Corp | Antifouling agent |
| CN102417556A (en) * | 2011-11-22 | 2012-04-18 | 上海氯碱化工股份有限公司 | Method for preparing vinyl chloride-vinyl acetate copolymer paste resin |
| CN105111350A (en) * | 2015-08-28 | 2015-12-02 | 江苏科技大学 | Terpolymer emulsion containing 1-vinyl iminazole and preparation method thereof |
-
2015
- 2015-10-08 CN CN201510644598.2A patent/CN105237671A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106961A (en) * | 1999-10-01 | 2001-04-17 | Tosoh Corp | Antifouling agent |
| CN102417556A (en) * | 2011-11-22 | 2012-04-18 | 上海氯碱化工股份有限公司 | Method for preparing vinyl chloride-vinyl acetate copolymer paste resin |
| CN105111350A (en) * | 2015-08-28 | 2015-12-02 | 江苏科技大学 | Terpolymer emulsion containing 1-vinyl iminazole and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111350A (en) * | 2015-08-28 | 2015-12-02 | 江苏科技大学 | Terpolymer emulsion containing 1-vinyl iminazole and preparation method thereof |
| CN105111350B (en) * | 2015-08-28 | 2017-05-03 | 江苏科技大学 | Terpolymer emulsion containing 1-vinyl iminazole and preparation method thereof |
| CN105585907A (en) * | 2016-03-02 | 2016-05-18 | 无锡雅邦化学有限公司 | Corrosion-inhibition anticorrosive paint with chlorine-containing polymer emulsion |
| CN105969103A (en) * | 2016-07-12 | 2016-09-28 | 广州中海环保科技有限公司 | Vinyl chloride-vinyl acetate-vinyl ester ternary polymer water-based resin |
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