CN102746437A - Method for improving water-solubility of polyethylene with high degree of polymerization - Google Patents
Method for improving water-solubility of polyethylene with high degree of polymerization Download PDFInfo
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- CN102746437A CN102746437A CN2012102543840A CN201210254384A CN102746437A CN 102746437 A CN102746437 A CN 102746437A CN 2012102543840 A CN2012102543840 A CN 2012102543840A CN 201210254384 A CN201210254384 A CN 201210254384A CN 102746437 A CN102746437 A CN 102746437A
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Abstract
The invention discloses a method for improving water-solubility of polyethylene with high degree of polymerization, which is characterized in that 3-10 parts of methanol solution of polyvinyl acetate with concentration of 10%-25% and degree of polymerization of 300-500 and 87-100 parts of methanol solution of polyvinyl acetate with concentration of 10%-25% and degree of polymerization of 1600-2400 are added into a reaction kettle equipped with a stirrer, a thermometer and a reflux condenser, and mixed with agitation speed of 200-1000 rev/min to enable the solution to be uniform; the temperature is slowly heated to 40-50 DEG C; 3-8 parts of methanol solution of 10% sodium hydroxide is added at one time to the reaction kettle for alcoholysis for 2-15min; white insoluble polyvinyl alcohol is produced; the polyvinyl alcohol is subjected to standing and heat insulation for 1.5-3h at the temperature of 40-50 DEG C to enable alcoholysis to be carried out completely; and then white polyvinyl alcohol is obtained by filtering, washed by methanol for 3 times, and placed in an oven at the temperature of 40-60 DEG for drying, so taht the water-solubility improved polyethylene with high degree of polymerization is obtained.
Description
Technical field
The present invention relates to a kind of water miscible method of polyvinyl alcohol of high degree of polymerization of improving, belong to the preparation field of high molecular polymer.
Technical background
Z 150PH is the polymkeric substance of synthetic that can be water-soluble few in number; Have unique powerful cementability, epithelium snappiness, smoothness, solvent resistance, protective colloid property, gas barrier performance and wear resistance, be widely used in industries such as iron and steel, papermaking, weaving, food, building, wood working.The Z 150PH commodity are generally powder or particle, when processing or use, carry out with aqueous solution state usually, and relate to the dissolving of Z 150PH.Z 150PH forms hydrogen bond and crystallization easily owing to have the poly-hydroxy characteristic, and the solvability in water is bad.Particularly the polymerization degree is higher, and the Z 150PH that alcoholysis degree is higher needs swelling in cold water earlier usually, is heated to then about 90 ℃, and stirring certain hour could dissolve fully.Therefore, improve the water-soluble of Z 150PH, be the problem that receives much concern for the user brings more convenience always.
Improve the water miscible method of Z 150PH chemical modification and physically modified are arranged.Chemical modification comprises modification by copolymerization and afterreaction modification, through changing the chemical structure of Z 150PH molecular chain, introduces other suitable groups and reduces intramolecularly and intermolecular hydrogen bond action, reaches and improves the water miscible purpose of Z 150PH; Chinese patent CN101081880A has reported a kind of preparation method of highly water-soluble polyvinyl alcohol, is characterized in vinyl acetate monomer and the vinyl monomer copolymerization that contains carboxyl or carboxamido-group, adds simultaneously to telomerize monomer and change the water-soluble of Z 150PH.The afterreaction modification is that Z 150PH is a raw material, under alkaline condition, carries out Michael reaction with acrylic ester compound, improves the water miscible purpose of Z 150PH thereby reach.
Physical modification method refers to blending and modifying, is about to other polymkeric substance or micromolecular compound and polyvinyl alcohol blending and reaches the water miscible purpose of improvement.As with starch blending, the preparation lesser temps under the dissolved Z 150PH.
Though physics or chemical modification method have improved the water-soluble of Z 150PH to a certain extent; But pass through the second-order transition temperature of the Z 150PH of chemical modification itself, melt temperature, decomposition temperature; Crystal property also changes thereupon, has influenced the physical and chemical performance of product.Blending and modifying is difficult to keep Z 150PH product performance completely owing to introduce the product of other blend components.Therefore, how to improve the water miscible character and the quality of Z 150PH product itself of guaranteeing simultaneously of Z 150PH and become a great problem.
Summary of the invention
The objective of the invention is to the deficiency of prior art and a kind of water miscible method of polyvinyl alcohol of high degree of polymerization of improving is provided; Be characterized in utilizing the principle of polyvinyl alcohol with low degree of polymerization plasticising polyvinyl alcohol of high degree of polymerization; Through regulating the ratio of low polymerization degree PVA in the high-polymerization degree PVA, realize improving the water-soluble of polyvinyl alcohol of high degree of polymerization through conventional alcoholysis method.The Z 150PH second-order transition temperature of preparation, melt temperature does not almost change, and the solvability in water is able to obvious improvement.
The object of the invention is by realizing that with technical measures wherein said raw material umber is parts by weight except that specified otherwise
The starting raw material that improves the water miscible method of polyvinyl alcohol of high degree of polymerization comprises following component:
Concentration is 10%～25%, the polymerization degree is 3～10 parts of 300～500 PVA methanol solutions
Concentration is 10%～25%, the polymerization degree is 87～100 parts of 1600～2400 PVA methanol solutions
Concentration is 3～8 parts of the methanol solutions of 10% sodium hydroxide
Improving the water miscible method of polyvinyl alcohol of high degree of polymerization may further comprise the steps:
With concentration be 10%～25%, the polymerization degree is that 300～500 3～10 parts of low polymerization degree PVA methanol solutions and concentration are 10%～25%, the polymerization degree is 87～100 parts of 1600～2400 high-polymerization degree PVA methanol solutions, adds to have in the reaction kettle of whisking appliance, TM and reflux exchanger, stir with 200～1000 rev/mins speed; Solution being mixed, slowly be warming up to 40～50 ℃, is 3～8 parts of the methanol solutions of 10% sodium hydroxide with concentration; In the disposable adding aforesaid reaction vessel, alcoholysis 2～15min, adularescent insolubles Z 150PH generates; In 40～50 ℃ of temperature; Leave standstill insulation 1.5～3h and make alcoholysis complete, filter out white polyethylene alcohol then, with methanol wash three times; Place the drying in oven of 40～60 ℃ of temperature, obtain water-soluble improved polyvinyl alcohol of high degree of polymerization.
The present invention has the following advantages:
1. the invention provides a kind of water miscible method of polyvinyl alcohol of high degree of polymerization of improving.With the Vinyl Acetate Copolymer ester solution of low polymerization degree and the PVA solution blending of high-polymerization degree, obtain modified polyvinyl alcohol through conventional alcoholysis then.
2. the Z 150PH produced of the present invention; Polyvinyl alcohol with low degree of polymerization and high-polymerization degree vinyl alcohol mixing have been realized at molecular level; Because the polyvinyl alcohol with low degree of polymerization molecular chain is prone to dissolving, thereby form the molecular channel, quicken water molecules to the polymkeric substance internal penetration; Shorten dissolution time, thereby realized improving the water miscible purpose of Vilaterm.
3. the Z 150PH produced of the present invention, it is water miscible very little to the physics of Z 150PH product own and chemical property and product gas purity influence simultaneously to have improved polyvinyl alcohol of high degree of polymerization, can guarantee the stability of product gas purity and capability and performance.
Embodiment
Through instance the present invention is specifically described below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can content make some nonessential improvement and adjustment to the present invention according to the present invention.
Embodiment 1
With concentration be 10%, the polymerization degree is that 3 parts of 300 PVA methanol solutions and concentration are 10%, the polymerization degree is 94 parts of 1600 PVA methanol solutions; Have in the reaction kettle of electronic stirring, TM, prolong common the adding; Elder generation makes it to mix with 300 rev/mins rotating speed stirred solution; When treating heating in water bath to 45 ℃; Be to carry out alcoholysis reaction in 3 parts of disposable adding reaction kettles of sodium hydrate methanol solution of 10% with concentration,, prevent that the Z 150PH that alcoholysis generates from becoming piece with the powerful stirred solution of 1000 rev/mins rotating speeds; Stop behind the alcoholysis reaction 10min stirring; 45 ℃ of water bath heat preservation 2h make alcoholysis complete. and filter out Z 150PH then and, dry by the fire 3h in 50 ℃ in baking oven and get the exsiccant Z 150PH with methanol wash three times. this modified polyvinyl alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, and 40min dissolves fully.
Embodiment 2
With concentration is that 10% polymerization degree is that 300 PVA methanol solutions are that 10% polymerization degree is 92 parts of 1600 PVA methanol solutions with concentration for 5 parts; Have in the reaction kettle of electronic stirring, TM, prolong common the adding; Earlier making it to mix with 300 rev/mins rotating speed stirred solution, when treating heating in water bath to 45 ℃, is to carry out alcoholysis reaction in 3 parts of disposable adding reaction kettles of sodium hydrate methanol solution of 10% with concentration; With the powerful stirred solution of 1000 rev/mins rotating speeds; Prevent that the Z 150PH that alcoholysis generates from becoming piece, stop behind the alcoholysis reaction 10min stirring that 45 ℃ of water bath heat preservation 2h make alcoholysis complete. filter out Z 150PH then and with methanol wash three times; 3h gets the exsiccant Z 150PH in 50 ℃ of bakings of baking oven. and this modified polyvinyl alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, and 30min dissolves fully.
Embodiment 3
With concentration be 10%, the polymerization degree is that 10 parts of 300 PVA methanol solutions and concentration are 10%, the polymerization degree is 87 parts of 1600 PVA methanol solutions; Have in the reaction kettle of electronic stirring, TM, prolong common the adding; Earlier making it to mix with 300 rev/mins rotating speed stirred solution, when treating heating in water bath to 45 ℃, is to carry out alcoholysis reaction in 3 parts of disposable adding reaction kettles of sodium hydrate methanol solution of 10% with concentration; With the powerful stirred solution of 1000 rev/mins rotating speeds; Prevent that the Z 150PH that alcoholysis generates from becoming piece, stop behind the alcoholysis reaction 10min stirring that 45 ℃ of water bath heat preservation 2h. filter out Z 150PH and then with methanol wash three times; In 50 ℃ in baking oven dry Z 150PH. this modified polyvinyl alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, and 26min dissolves fully.
Embodiment 4
With concentration be 25%, the polymerization degree is that 3 parts of 300 PVA methanol solutions and concentration are 25%, the polymerization degree is 100 parts of 2400 PVA methanol solutions; Have in the reaction kettle of electronic stirring, TM, prolong common the adding; Elder generation makes it to mix with 500 rev/mins rotating speed stirred solution; When treating heating in water bath to 45 ℃, be to carry out alcoholysis reaction in 8 parts of disposable adding reaction kettles of sodium hydrate methanol solution of 10% with concentration, solution mixed with powerful stirring of 1000 rev/mins rotating speeds; Stop behind the 2min stirring; 45 ℃ of water bath heat preservation 2.5h. filter out Z 150PH and then with methanol wash three times, in 50 ℃ in baking oven dry Z 150PH. this modified polyvinyl alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, and 1h dissolves fully.
Embodiment 5
With concentration be 15%, the polymerization degree is that 5 parts of 500 PVA methanol solutions and concentration are 15%, the polymerization degree is 95 parts of 1700 PVA methanol solutions; Have in the reaction kettle of electronic stirring, TM, prolong common the adding; Earlier making it to mix with 300 rev/mins rotating speed stirred solution, when treating heating in water bath to 45 ℃, is to carry out alcoholysis reaction in 4.5 parts of disposable adding reaction kettles of sodium hydrate methanol solution of 10% with concentration; With the powerful stirred solution of 1000 rev/mins rotating speeds; Prevent that the Z 150PH that alcoholysis generates from becoming piece, stop behind the alcoholysis reaction 15min stirring that 45 ℃ of water bath heat preservation 2h. filter out Z 150PH and then with methanol wash three times; In 50 ℃ in baking oven dry Z 150PH. this modified polyvinyl alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, and 35min dissolves fully.
Comparative Examples 1
With concentration be 10%, the polymerization degree is that 100 parts of addings of 1600 PVA methanol solutions have in the reaction kettle of electronic stirring, TM, prolong; Elder generation stirs with 300 rev/mins rotating speed; When treating heating in water bath to 45 ℃; Be to carry out alcoholysis reaction in 3 parts of disposable adding reaction kettles of sodium hydrate methanol solution of 10% with concentration,, prevent that the Z 150PH that alcoholysis generates from becoming piece with the powerful stirred solution of 1000 rev/mins rotating speeds; Stop behind the alcoholysis reaction 10min stirring; 45 ℃ of water bath heat preservation 2h. filter out Z 150PH and then with methanol wash three times, in 50 ℃ in baking oven dry Z 150PH. this unmodified polyethylene alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, dissolving need 1h.Compare with embodiment 1～3, the dissolution time of the more unmodified Z 150PH of modified polyethylene alcohol has shortened half the.
Comparative Examples 2
With concentration be 25%, the polymerization degree is that 100 parts of addings of 2400 PVA methanol solutions have in the reaction kettle of electronic stirring, TM, prolong; Elder generation stirs with 500 rev/mins rotating speed; When treating heating in water bath to 45 ℃, be to carry out alcoholysis reaction in 7.5 parts of disposable adding reaction kettles of methanol solution of 10% sodium hydroxide with concentration, solution mixed with powerful stirring of 1000 rev/mins rotating speeds; Stop behind the 2min stirring; 45 ℃ of water bath heat preservation 2h. filter out Z 150PH and then with methanol wash three times, in 50 ℃ in baking oven dry Z 150PH. this unmodified polyethylene alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, and 1.5h dissolves fully.Compare with embodiment 4, the dissolution time of the more unmodified Z 150PH of modified polyethylene alcohol has shortened half the.
Comparative Examples 3
With concentration be 15%, the polymerization degree is that 100 parts of addings of 1700 PVA methanol solutions have in the reaction kettle of electronic stirring, TM, prolong; Elder generation stirs with 300 rev/mins rotating speed; When treating heating in water bath to 45 ℃; Be to carry out alcoholysis reaction in 4.5 parts of disposable adding reaction kettles of methanol solution of 10% sodium hydroxide with concentration,, prevent that the Z 150PH that alcoholysis generates from becoming piece with the powerful stirred solution of 1000 rev/mins rotating speeds; Stop behind the alcoholysis reaction 15min stirring; 45 ℃ of water bath heat preservation 2h. filter out Z 150PH and then with methanol wash three times, in 50 ℃ in baking oven dry Z 150PH. this unmodified polyethylene alcohol places 90 ℃ of constant temperature deionized water magnetic agitation, dissolving need 1h.Compare with embodiment 5, the dissolution time of the more unmodified Z 150PH of modified polyethylene alcohol has shortened near half the.
Claims (2)
1. one kind is improved the water miscible method of polyvinyl alcohol of high degree of polymerization, it is characterized in that the starting raw material of this method comprises following component, and counts by weight:
Concentration is 10%～25%, the polymerization degree is 3～10 parts of 300～500 PVA methanol solutions
Concentration is 10%～25%, the polymerization degree is 87～100 parts of 1600～2400 PVA methanol solutions
Concentration is 3～8 parts of the methanol solutions of 10% sodium hydroxide.
2. improve the water miscible method of polyvinyl alcohol of high degree of polymerization according to claim 1, it is characterized in that this method may further comprise the steps:
With concentration be 10%～25%, the polymerization degree is that 3～10 parts of 300～500 PVA methanol solutions and concentration are 10%～25%, the polymerization degree is 87～100 parts of 1600～2400 PVA methanol solutions, adds to have in the reaction kettle of whisking appliance, TM and reflux exchanger, stir with 200～1000 rev/mins speed; Solution being mixed, slowly be warming up to 40～50 ℃, is 3～8 parts of the methanol solutions of 10% sodium hydroxide with concentration; In the disposable adding aforesaid reaction vessel, alcoholysis 2～15min, adularescent insolubles Z 150PH generates; In 40～50 ℃ of temperature; Leave standstill insulation 1.5～3h and make alcoholysis complete, filter out white polyethylene alcohol then, with methanol wash three times; Place the drying in oven of 40～60 ℃ of temperature, obtain water-soluble improved polyvinyl alcohol of high degree of polymerization.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558308A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工集团公司 | Production method of low-density instant PVA product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040988A (en) * | 2009-10-09 | 2011-05-04 | 中国石油化工集团公司 | Oil field well cementation filtration-reducing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040988A (en) * | 2009-10-09 | 2011-05-04 | 中国石油化工集团公司 | Oil field well cementation filtration-reducing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张军科，惠学洲: "高聚合度PVAc醇解工艺研究", 《化学工程师》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558308A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工集团公司 | Production method of low-density instant PVA product |
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Application publication date: 20121024 |