CN101311196A - Method for preparing ethylene-vinyl esters copolymer water-soluble emulsion and ethylene-vinyl ester copolymer water-soluble emulsion - Google Patents
Method for preparing ethylene-vinyl esters copolymer water-soluble emulsion and ethylene-vinyl ester copolymer water-soluble emulsion Download PDFInfo
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- CN101311196A CN101311196A CNA2007101051617A CN200710105161A CN101311196A CN 101311196 A CN101311196 A CN 101311196A CN A2007101051617 A CNA2007101051617 A CN A2007101051617A CN 200710105161 A CN200710105161 A CN 200710105161A CN 101311196 A CN101311196 A CN 101311196A
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Abstract
The invention provides a preparation method for the ethylene-vinyl ester copolymer water-base emulsion with favorable water resistance and high content of non-volatile component and the ethylene-vinyl ester polymer water-base emulsion with the performance prepared by the method. The method is a method for preparing the ethylene-vinyl ester polymer water-base emulsion by polymerizing ethylene and vinyl ester under the existence of at least 2 polyvinyl alcohols and inorganic oxidation reduction system polymerization catalysts with different polymerization degrees; wherein, the total application amount of the polyvinyl alcohol is that each 100 mass portions of polyvinyl alcohol adopt 3-10 mass portions of vinyl ester and the gel fraction of the obtained polymer is 25-50 mass percent.
Description
Technical field
It is high and can form the manufacture method of ethylene-vinyl ester copolymer water-soluble emulsion of tunicle of water tolerance excellence and the ethylene-vinyl ester copolymer water-soluble emulsion that adopts this manufacture method to make to the present invention relates to nonvolatile component content.
Background technology
To be used for the caking agent of paper and paper, when caking agent is used in covering, have the problem of poor water resistance as the water-based emulsion of main component with ethylene-vinyl ester copolymer.So far, in order to address these problems, proposed to improve the manufacture method of the acetate unit content of ethylene-vinyl ester copolymer, this manufacture method is by improving ethylene partial pressure, and the content that makes vinyl ester in the reaction soln is below the 10 weight %, thereby improve acetate unit content (for example, with reference to patent documentation 1).But, for this manufacture method, with general be that the manufacture method of main component water-based emulsion is compared with the ethylene-vinyl ester copolymer, discarded ethene amount increases, manufacturing time prolongations etc. have problems aspect economy and industrial production.
In addition, technical intelligence as manufacturers, carried out the change converging operation, perhaps improved the trial of the acetate unit content in the water-based emulsion, but have practicality with the ethylene-vinyl ester copolymer be main component the water tolerance excellence water-based emulsion manufacture method as yet the report.
Patent documentation 1: the spy opens the 2002-322216 communique
Summary of the invention
Even the object of the present invention is to provide the ethylene content identical with existing ethylene-vinyl ester copolymer, nonvolatile component content is high and also can form the manufacture method of ethylene-vinyl ester copolymer water-soluble emulsion of tunicle of water tolerance excellence and the ethylene-vinyl ester copolymer water-soluble emulsion with above-mentioned performance.
The present inventor has carried out research with keen determination to achieve these goals repeatedly.It found that, the specified quantitative of at least 2 kinds of different polyvinyl alcohol of the polymerization degree and inorganic oxide reduction be polymerizing catalyst in the presence of, make ethene and vinyl ester copolymerization, and the gel fraction of this multipolymer is 25～50% o'clock, obtain the good ethylene-vinyl ester copolymer water-soluble emulsion of water tolerance, according to this experience, finished the present invention.
That is, the present invention relates to:
(1) manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of water tolerance, be the different at least 2 kinds of polyvinyl alcohol of the polymerization degree and inorganic oxide reduction be polymerizing catalyst in the presence of, make ethene and vinyl ester copolymerization make the method for ethylene-vinyl ester copolymer water-soluble emulsion, it is characterized in that: total usage quantity of above-mentioned polyvinyl alcohol is per 100 mass parts vinyl ester, 3～10 mass parts, and the gel fraction of the multipolymer that obtains is 25～50 quality %.
(2) manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of above-mentioned (1) described water tolerance, wherein, as described at least 2 kinds of polyvinyl alcohol, use more than or equal to the polyvinyl alcohol of a kind of polymerization degree 400～1400 with more than or equal to the polyvinyl alcohol of a kind of polymerization degree 1400～3500.
(3) manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of above-mentioned (1) or (2) described water tolerance, wherein, the proportioning of described at least 2 kinds of polyvinyl alcohol (mass ratio) is polyvinyl alcohol=1/2～20/1 of the polyvinyl alcohol/polymerization degree 1400～3500 of the polymerization degree 400～1400.
(4) manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of each described water tolerance of above-mentioned (1)～(3), wherein, nonvolatile component is 50～72 quality %.
(5) the good ethylene-vinyl ester copolymer water-soluble emulsion of water tolerance that uses each described manufacture method of above-mentioned (1)～(4) to obtain.
According to the present invention, even the ethylene content identical with existing ethylene-vinyl ester copolymer can be provided, nonvolatile component content is high and also can form the manufacture method of ethylene-vinyl ester copolymer water-soluble emulsion of tunicle of water tolerance excellence and the ethylene-vinyl ester copolymer water-soluble emulsion with above-mentioned performance.In addition, the affinity excellence of difficult bonding planes such as water-based emulsion that makes and polyolefine can be as caking agent, pressure sensitive adhesive or these properties-correcting agent, these basic emulsion use.
Embodiment
Below the present invention is described in detail.
Manufacture method of the present invention is to be the manufacture method of the water-based emulsion of main component with the ethylene-vinyl ester copolymer, and described ethylene-vinyl ester copolymer obtains by ethene and vinyl ester are carried out letex polymerization.
Specifically, can enumerate for example following method: but monomer of water, at least 2 kinds of polyvinyl alcohol, vinyl ester, copolymerization as required etc. in pressure-resistant reaction vessel, added, after being warmed up to the setting temperature of reaction, replace reaction vessel with ethene on the limit, ethene is pressurizeed, the concentration of vinyl ester in the reaction soln of copolymerization is regulated on the limit, adds the reduction of above-mentioned vinyl ester and inorganic oxide and is polymerizing catalyst etc. and carry out copolymerization.
As the vinyl ester that uses among the present invention (monomer), can enumerate for example alkyl acid vinyl acetate such as vinyl acetate, vinyl butyrate, propionate, new vinyl acetate acid, vinyl laurate, different n-nonanoic acid vinyl acetate, tertiary carboxylic acid vinyl acetate etc.In addition, as vinyl ester, can use the vinyl ester more than 2 kinds.In vinyl ester, preferred vinyl acetate.
As the monomer that uses in the manufacture method of the present invention, except ethene, vinyl ester, can use can with the monomer of their copolymerization, specifically, can enumerate ethylene halides such as vinylchlorid, bromine ethene; Vinylidene chloride isogonic halogen vinyl; Vinyl phosphonate, vinyl sulfonic acid and their vinyl compounds such as salt; Aromatic ethenyl compounds such as vinylbenzene, alpha-methyl styrene, chloro-styrene; Methacrylic acid, vinylformic acid etc. (methyl) vinylformic acid; (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester; α such as toxilic acid, maleic anhydride, succsinic acid, methylene-succinic acid, β-unsaturated dicarboxylic acid class; Nitriles such as (methyl) vinyl cyanide; Acrylic amides such as N hydroxymethyl acrylamide, N-butoxymethyl acrylamide; Divinyl, isoprene equiconjugate dienes; Allylic cpds such as sulfonic acid allyl ester, Phthalic acid, diallyl ester, triallyl cyanurate, triallyl isocyanurate; Polyfunctional acrylic esters such as pentaerythritol triacrylate, tetramethylol methane tetraacrylate, tetramethylolmethane six acrylate, Viscoat 295 etc.These the 3rd comonomer classes can also be used separately or more than 2 kinds in the scope of not damaging the object of the invention.
At least 2 kinds the polyvinyl alcohol that uses among the present invention, use its polymerization degree more than a kind be 400～1400 polyvinyl alcohol and more than a kind the polymerization degree be 1400～3500 polyvinyl alcohol, the polymerization degree of the latter's polyvinyl alcohol is than the polymerization degree height of the former polyvinyl alcohol.In addition, preferred 70 moles more than the % of the saponification deg of this polyvinyl alcohol, the ratio of the former polyvinyl alcohol and the latter's polyvinyl alcohol (mass ratio) is preferred 1/2～20/1, and more preferably 1/1.5～15/1.This ratio is 1/2 when above, obtains the water-based emulsion of good stability.In addition, be 20/1 to obtain the water-based emulsion of good stability when following too.This polyvinyl alcohol can be according to purpose with a part of modification with the hydroxyl of polyvinyl alcohol such as the compound of carboxylic acid, sulfonic acid, siloxanes, alkyl etc.
The polymerization degree is that 400～1400 polyvinyl alcohol has effect for improving ethylene content, but only the water-based emulsion that obtains with the polyvinyl alcohol of the polymerization degree 400～1400 more than a kind become not enough by film toughness, therefore must and with the polyvinyl alcohol of the polymerization degree 1400～3500 more than a kind.
Wherein, if use the polyvinyl alcohol of the polymerization degree below 400, can't reach practical required by film toughness, if use the polyvinyl alcohol more than 3500 on the contrary, the viscosity of reaction soln raises, the content that can't obtain ethylene unit is the above ethylene-vinyl ester copolymers of 30 quality %, and the flexibility variation of tunicle is difficult to obtain the such performance as the high ethylene-vinyl ester copolymer of acetate unit content of adaptation, low temperature degree of stretching with polyolefine etc.
Total usage quantity of polyvinyl alcohol is employed vinyl ester 3～10 mass parts of per 100 mass parts, is preferably 2～8 mass parts.By using more than 3 mass parts, obtain the emulsion of good stability, by becoming below 10 mass parts, the viscosity of the water-based emulsion that obtains has practicality, have practicality by film toughness.
The polymerizing catalyst that uses in the manufacture method of the present invention, the inorganic oxide reduction of being made up of Oxidizing and Reducing Agents is a polymerizing catalyst.As this oxygenant, can enumerate for example Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc., as this reductive agent, can enumerate for example sodium bisulfite, sodium metabisulfite, Sulfothiorine etc.
The usage quantity of this oxygenant, is counted about 0.1～10 mass parts preferred 0.2～6 mass parts with respect to vinyl ester 100 mass parts with mixture.
The usage quantity of this reductive agent, is counted about 0.1～10 mass parts preferred 0.2～6 mass parts with respect to vinyl ester 100 mass parts with mixture.
The dividing potential drop of ethene is 1～10MPa in the copolyreaction, is preferably 3～8MPa.Be pressed in this scope if divide, reduction of the content of the ethylene unit in the multipolymer that can occur obtaining or reaction times do not become long situation, needn't improve the resistance to pressure of employed reaction vessel yet.
As the temperature of reaction of copolyreaction, be generally about 40～85 ℃ preferred 50～70 ℃.Do not become long situation if the reaction times in this scope, also can not appear in temperature of reaction, can prevent that the content that reduces the ethylene unit in the multipolymer that produces because of ethene meltage in the reaction soln from reducing.
By using at least 2 kinds of polyvinyl alcohol, adopting and having utilized the inorganic oxide reduction is the ethylene-vinyl ester copolymer that the copolyreaction of polymerizing catalyst makes, and has 25～50%, preferred 30～45% gel fraction.If gel fraction in 25～50% scope, the situation of water tolerance variation can not occur, nor the situation that can occur making the film variation and can't obtain required bonding force.In addition, adopting the nonvolatile component of the ethylene-vinyl ester copolymer water-soluble emulsion that manufacture method of the present invention obtains is 50～72%, is preferably 55～65%.If nonvolatile component in 50～72% scope, thereby the time-consuming situation of not having a practicality of dried floral can not appear, do not accelerate and do not have a situation of practicality thereby surface drying can not occur yet.
Wherein, so-called nonvolatile component is meant water intaking property emulsion 1g, accurately after the weighing, 105 ℃ of temperature dry 1 hour down, with quality ratio (%) expression of the dry thing that obtains with respect to the water-based emulsion of being got.。
As the content of ethylene unit in the gained multipolymer, with respect to copolymer 1 00 quality %, ethylene unit is about 5～40 quality % usually, preferred 10～30 quality %.
Wherein, the Determination on content of ethylene unit, be with multipolymer integral body as 100%, measure the content of vinyl ester units in the multipolymer with proton N MR method, by deducting this value, obtain the content of ethylene unit.
In ethylene-vinyl ester copolymer water-soluble emulsion of the present invention, can add PH conditioning agent, defoamer, sanitas, membrane producing promoter, filler, whipping agent, tackifier, viscosity modifier, fire retardant, pigment etc. such as ammoniacal liquor, thanomin according to purpose.
Embodiment
The present invention is described in detail below to use embodiment, but following embodiment all do not limit of the present invention, implements then all to be included in the technical scope of the present invention in the scope that does not break away from the content of being put down in writing.In addition, if no special instructions, part, % represent mass parts, quality % respectively.
Below the method for evaluating performance that adopts the water-based emulsion that the present invention makes is described.
(1) measuring method of gel fraction
Under 23 ℃ atmosphere water-based emulsion placed and made film in 5 days, it is thick to make resin coating reach about 0.3mm, then, in Vacuumdrier, under the reduced pressure of 101kPa, drying 2 hours.
The resin coating that obtains is cut into the square of 2cm * 2cm, accurate its quality of weighing (W1) is put into the vial of the about 100ml of internal volume with this tunicle, impregnated under 23 ℃ in the benzene after 24 hours, under 105 ℃ with dry 1 hour of tunicle, accurate its quality of weighing (W2).
Gel fraction (quality %)=W2/W1 * 100
(2) measuring method of water tolerance (water-fast solubility rate)
Under 23 ℃ atmosphere water-based emulsion placed and made film in 5 days, it is thick to make resin coating reach about 0.3mm, then, in Vacuumdrier, under the reduced pressure of 101kPa, drying 2 hours.
The resin coating that obtains is cut into the square of 2cm * 2cm, and accurate its quality of weighing (W1) is put into the vial of the about 100ml of internal volume, impregnated in the water 24 hours under 23 ℃.Then, under 105 ℃ with dry 1 hour of tunicle, accurate its quality of weighing (W2).
Water-fast solubility rate (%)=(W1-W2)/W1 * 100
Embodiment 1
In the stainless die autoclave of 1.5 liters of the internal volumes with anchor stirrer, the distilled water of packing into, 396 parts of vinyl acetates, 12 parts of polyvinyl alcohol " Port バ one Le 205 " (Kuraray Co., Ltd.'s system, 88 moles of % of saponification deg, mean polymerisation degree 500), 12 parts of " Port バ one Le 217 " (Kuraray Co., Ltd.'s system, 88 moles of % of saponification deg, mean polymerisation degree 1700), 1.5 parts of sodium bisulfites (SBS, reductive agent).Then, with ethene the air in the autoclave is fully replaced.
Under agitation, polymerization temperature is elevated to 60 ℃, ethylene pressure is boosted to 5MPa.Then, with adding 0.5 part of ammonium persulphate (APS, oxygenant) in 8 hours equably.In addition, add 99 parts of vinyl acetates equably with 6 hours simultaneously, carry out copolyreaction.Catalyzer cools off after adding end, adds defoamer, wetting agent, tackifier, sanitas, mould inhibitor and pH regulator agent, makes the ethylene-vinyl acetate copolymer water-based emulsion.The acetate unit content of the water-based emulsion that obtains is 12%, and nonvolatile component is 55%, and viscosity is 6000mPas.Adopt above-mentioned method of evaluating performance that gel fraction, the water-fast solubility rate (water tolerance) of the water-based emulsion that makes are estimated, be shown in table 1.
Embodiment 2～4
Except usage quantity, the Oxidizing and Reducing Agents of " Port バ one Le 205 " that make polyvinyl alcohol, " Port バ one Le 217 " are as shown in table 1, carry out copolymerization according to embodiment 1.
The acetate unit content of the water-based emulsion that obtains among the embodiment 2 is 13%, and nonvolatile component is 55%, and viscosity is 4000mPas.
The acetate unit content of the water-based emulsion that obtains among the embodiment 3 is 12%, and nonvolatile component is 55%, and viscosity is 5500mPas.
The acetate unit content of the water-based emulsion that obtains among the embodiment 4 is 12%, and nonvolatile component is 55%, and viscosity is 6000mPas.
Adopt above-mentioned method of evaluating performance that gel fraction, the water-fast solubility rate (water tolerance) of the water-based emulsion that makes are estimated, be shown in table 1.
Comparative example 1
The vinyl acetate that adds in the autoclave when polymerization is begun becomes 495 especially by 396 parts, carries out copolymerization according to embodiment 1.The acetate unit content of the water-based emulsion that obtains is 10%, and nonvolatile component is 54%, and viscosity is 4000mPas.Adopt above-mentioned method of evaluating performance that gel fraction, the water-fast solubility rate (water tolerance) of the water-based emulsion that makes are estimated, be shown in table 1.
Comparative example 2
Except making employed polyvinyl alcohol as shown in table 1, making temperature of reaction is outside 80 ℃, carries out copolymerization according to embodiment 1.The acetate unit content of water-based emulsion is 12%, and nonvolatile component is 55%, and viscosity is 6000mPas.
Comparative example 3～4
Except usage quantity, the Oxidizing and Reducing Agents of " Port バ one Le 205 " that make polyvinyl alcohol, " Port バ one Le 217 " are as shown in table 1, carry out copolymerization according to embodiment 1.
The acetate unit content of the water-based emulsion that obtains in the comparative example 3 is 12%, and nonvolatile component is 55%, and viscosity is 5500mPas.
The acetate unit content of the water-based emulsion that obtains in the comparative example 4 is 12%, and nonvolatile component is 55%, and viscosity is 6000mPas.
Adopt above-mentioned method of evaluating performance that gel fraction, the water-fast solubility rate (water tolerance) of the water-based emulsion that makes are estimated, be shown in table 1.
Table 1
Annotate) APS: ammonium persulphate
KPS: Potassium Persulphate
HPO: hydrogen peroxide
SBS: sodium bisulfite
SMBS: sodium metabisulfite
TA: tartrate
ASA: xitix
Even the present invention can provide the ethylene content identical with existing ethylene-vinyl ester copolymer, nonvolatile component is high and also can form the manufacture method of ethylene-vinyl ester copolymer water-soluble emulsion of tunicle of water tolerance excellence and the ethylene-vinyl ester copolymer water-soluble emulsion with above-mentioned performance.In addition, the affinity excellence of difficult bonding planes such as water-based emulsion that makes and polyolefine can be as caking agent, pressure sensitive adhesive or these properties-correcting agent, these basic emulsion use.
Claims (5)
1. the manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of water tolerance, be the different at least 2 kinds of polyvinyl alcohol of the polymerization degree and inorganic oxide reduction be polymerizing catalyst in the presence of, make ethene and vinyl ester copolymerization make the method for ethylene-vinyl ester copolymer water-soluble emulsion, it is characterized in that: total usage quantity of above-mentioned polyvinyl alcohol is per 100 mass parts vinyl ester, 3～10 mass parts, and the gel fraction of the multipolymer that obtains is 25～50 quality %.
2. the manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of the described water tolerance of claim 1, wherein, as described at least 2 kinds of polyvinyl alcohol, use more than or equal to the polyvinyl alcohol of a kind of polymerization degree 400～1400 with more than or equal to the polyvinyl alcohol of a kind of polymerization degree 1400～3500.
3. the manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of the described water tolerance of claim 1, wherein, the proportioning of described at least 2 kinds of polyvinyl alcohol (mass ratio) is polyvinyl alcohol=1/2～20/1 of the polyvinyl alcohol/polymerization degree 1400～3500 of the polymerization degree 400～1400.
4. the manufacture method of the good ethylene-vinyl ester copolymer water-soluble emulsion of the described water tolerance of claim 1, wherein, nonvolatile component is 50～72 quality %.
5. the good ethylene-vinyl ester copolymer water-soluble emulsion of water tolerance that uses each described manufacture method of claim 1～4 to obtain.
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| CN103724513A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工集团公司 | Modified polyvinyl alcohol and preparation method thereof |
| CN103724514A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工集团公司 | Preparation method for vinyl modified polyvinyl alcohol |
| CN105820285A (en) * | 2014-12-29 | 2016-08-03 | 周大胜 | Vinyl chloride copolymer latex with salt fog resistance |
| CN105859944A (en) * | 2014-12-29 | 2016-08-17 | 周大胜 | Salt fog resistance vinylidene chloride copolymer latex |
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| CN103724513A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工集团公司 | Modified polyvinyl alcohol and preparation method thereof |
| CN103724514A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工集团公司 | Preparation method for vinyl modified polyvinyl alcohol |
| CN103724514B (en) * | 2012-10-12 | 2016-03-02 | 中国石油化工集团公司 | A kind of preparation method of vinyl modified polyvinyl alcohol |
| CN103724513B (en) * | 2012-10-12 | 2016-04-27 | 中国石油化工集团公司 | A kind of modified polyvinyl alcohol and preparation method thereof |
| CN105924560A (en) * | 2014-12-29 | 2016-09-07 | 周大胜 | Salt-fog-resistant vinylidene chloride copolymer latex |
| CN105859944A (en) * | 2014-12-29 | 2016-08-17 | 周大胜 | Salt fog resistance vinylidene chloride copolymer latex |
| CN105820285A (en) * | 2014-12-29 | 2016-08-03 | 周大胜 | Vinyl chloride copolymer latex with salt fog resistance |
| CN105924560B (en) * | 2014-12-29 | 2017-12-19 | 谢长溪 | A kind of metachloroethylene copolymer latex of salt fog resistance |
| CN105820285B (en) * | 2014-12-29 | 2018-01-05 | 揭伟 | A kind of metachloroethylene copolymer latex of salt fog resistance |
| CN105859944B (en) * | 2014-12-29 | 2018-01-19 | 浙江海威信新材料科技有限公司 | A kind of metachloroethylene copolymer latex of salt fog resistance |
| US11214609B2 (en) | 2017-09-28 | 2022-01-04 | Geltor, Inc. | Recombinant collagen and elastin molecules and uses thereof |
| US11168126B2 (en) | 2019-04-12 | 2021-11-09 | Geltor, Inc. | Recombinant elastin and production thereof |
| CN113956387A (en) * | 2021-11-02 | 2022-01-21 | 安徽皖维高新材料股份有限公司 | Copolymerization modified polyvinyl alcohol and preparation method thereof |
| CN113956387B (en) * | 2021-11-02 | 2023-05-26 | 安徽皖维高新材料股份有限公司 | Copolymerization modified polyvinyl alcohol and preparation method thereof |
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