CN111072800A - Modified ultra-high molecular weight polyvinyl alcohol and preparation method and application thereof - Google Patents
Modified ultra-high molecular weight polyvinyl alcohol and preparation method and application thereof Download PDFInfo
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- CN111072800A CN111072800A CN201911239942.4A CN201911239942A CN111072800A CN 111072800 A CN111072800 A CN 111072800A CN 201911239942 A CN201911239942 A CN 201911239942A CN 111072800 A CN111072800 A CN 111072800A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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Abstract
The invention belongs to the field of modified PVA, and particularly relates to modified polyvinyl alcohol with ultrahigh molecular weight, and a preparation method and application thereof. The preparation method of the modified ultra-high molecular weight polyvinyl alcohol comprises the following steps: adding polyvinyl alcohol powder into a reaction kettle, continuously adding a certain amount of solvent as a reaction carrier, heating, stirring, adding a modifier, and washing and drying a product by using a washing solvent after the reaction is finished to obtain the modified polyvinyl alcohol with the ultrahigh molecular weight. The invention aims to obtain a polyvinyl alcohol product with ultrahigh polymerization degree through chemical modification, the molecular weight is increased through crosslinking, and double bonds are added on a polymer chain, so that the activity can be improved, and the application of the polyvinyl alcohol product as a reaction type auxiliary agent is facilitated, such as: the emulsion polymerization of vinyl monomers takes part in the reaction. Meanwhile, compared with the traditional polyvinyl alcohol, the structure increases the hydrophobic result after crosslinking, and is beneficial to the water resistance of the polyvinyl alcohol.
Description
Technical Field
The invention belongs to the field of modified PVA, and particularly relates to modified polyvinyl alcohol with ultrahigh molecular weight, and a preparation method and application thereof.
Background
Polyvinyl alcohol (PVA) is a water-soluble polymer, and its special properties make it widely used. For example: textile industry, construction industry, coating field, adhesives field, electronic ceramics, etc. Particularly in the field of Vinyl Acetate Emulsion (VAE) manufacture, polyvinyl alcohol is widely used as a stabilizer or an additive after emulsion polymerization in vinyl acetate emulsion polymerization, and compared with other stabilizers, the polyvinyl alcohol emulsion has the advantages of high viscosity, good mechanical stability, high film strength, good heat resistance and the like; however, the water resistance of the adhesive or film blended with the emulsion is reduced due to the large addition amount of the polyvinyl alcohol, and the manufacturing cost of the emulsion is increased due to the large addition amount of the polyvinyl alcohol.
On the other hand, in the field of textile sizing, the addition amount of the existing polyvinyl alcohol or modified starch is large, the COD (chemical oxygen demand) and BOD (biochemical oxygen demand) values of sewage are seriously influenced, and the environmental protection requirement is not met.
Most importantly: the current domestic polyvinyl alcohol manufacturing technology cannot produce polyvinyl alcohol with the polymerization degree of more than 3000 due to the double influence of the process technology and the cost.
Disclosure of Invention
The invention aims to provide modified polyvinyl alcohol with ultrahigh molecular weight, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of modified ultra-high molecular weight polyvinyl alcohol comprises the following steps: adding polyvinyl alcohol powder into a reaction kettle, continuously adding a certain amount of solvent as a reaction carrier, heating, stirring, adding a modifier, and washing and drying a product by using a washing solvent after the reaction is finished to obtain the modified polyvinyl alcohol with the ultrahigh molecular weight.
Specifically, the selected polyvinyl alcohol powder is used as a modified raw material, quantitatively added into a reaction kettle, continuously added with a quantitative solvent as a reaction carrier, heated to 30-90 ℃ and kept for 30-180 minutes; then, starting to add a quantitative modifier, adding the modifier in one step or in batches or dropwise adding the modifier at a certain speed, if the dropwise adding needs to be finished within 2.5 to 5 hours, continuously keeping the temperature of 30-90 ℃ unchanged and keeping the temperature for 2.5-8 hours, and discharging unreacted substances; then washing for 1 to 4 times by using a washing solvent with the weight being one to two times of that of the polyvinyl alcohol, and drying the solid material for 30 to 360 minutes at the temperature of between 40 and 125 ℃ after discharging the washing solvent to obtain the modified polyvinyl alcohol.
The mass ratio of the polyvinyl alcohol to the modifier is 100: 12-50.
The mass ratio of the polyvinyl alcohol, the modifier, the reaction carrier and the washing solvent is 100:12-50:15-45: 100-800.
The modifier is an enedioic acid monoester. Can be one or mixture of monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl maleate, monoethyl maleate or monobutyl maleate.
The washing solvent is one or a mixture of methanol, ethanol, propanol, isopropanol, butanol or methyl acetate, ethyl acetate, propyl acetate and butyl acetate; for economic reasons, one of methanol, methyl acetate or a mixture thereof is preferred.
The reaction carrier is as follows:
organic acids: formic acid, acetic acid (acetic acid), propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid or mixtures thereof.
Ketones: one or a mixture of acetone, butanone (methyl ethyl ketone), pentanone and methyl isobutyl ketone;
alkanes: hexane, dimethylpentane, 3-methylpentane, 2, 3-dimethylbutane and 2, 2-dimethylbutane or pentane or a mixture thereof.
Esters: methyl acetate, ethyl acetate, butyl acetate, amyl acetate; methyl propionate, ethyl propionate, butyl propionate, pentyl propionate; methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, amyl butyrate or a mixture thereof.
Preferably, the reaction carrier is: one or a mixture of acetic acid, propionic acid, acetone, hexane, methyl acetate, ethyl acetate, methyl propionate and methyl butyrate; for economic reasons, more preferred are: acetic acid, propionic acid, hexane, cyclohexane or mixtures thereof.
The reaction temperature is 30-90 ℃. Preferably, the reaction temperature is 45-70 ℃ and the reaction time is 3.0-6.5 hours.
The application also comprises the modified polyvinyl alcohol obtained by the preparation method, wherein the total solid content is as follows: greater than 95.0%; alcoholysis degree mole% range: 75 mole% to 95 mole%; viscosity of 4% aqueous solution at 20 ℃ mPa.s: 90.0-250.0.
The drying method of the modified polyvinyl alcohol with ultrahigh polymerization degree comprises the following steps:
the drying process consists of 3 stages; the first stage is a pre-heating stage of the gel particles of the wet mass, where the mass is heated to the evaporation temperature of the volatiles. The second stage is a constant rate drying stage, where the volatiles on the surface of the wet particles evaporate, the drying rate does not change, and the temperature of the material does not rise. The third stage is a deceleration drying stage, in which the volatile matter inside the wet particles is evaporated, the drying rate is gradually decreased, and the material is heated to the air temperature inside the dryer.
In general, the drying rate (volatile evaporation rate) is as follows. S-evaporation area in formula, m2(ii) a G-supply of wet material, kg/h; u-drying Rate, kg/m2·h；
The drying time can be calculated by the formula (2). In the formula, X0-weight ratio of volatiles to mass at the beginning of drying; xτ-the weight ratio of volatiles to feed at time τ;
the above formula was used to verify the drying experiment results. The drying temperature is controlled as follows: 40-125 ℃; preferably 60-115 deg.C.
The coating agent is applied to a formed object, an adhesive, a coating agent, a suspension dispersion stabilizer, an emulsion dispersion stabilizer, a thickener, a flocculant, a soil conditioner, a photosensitizer, or a photosensitive resist resin.
(1) Forming products: fibers, films, sheets, straws (pipe), tubes (tube), leakage-proof membranes, temporary coatings, water-soluble fibers, and the like.
(2) Adhesive agent: adhesives such as wood, paper, aluminum foil, and plastic, adhesives, rewetting agents, adhesives for nonwoven fabrics, adhesives for various building materials such as gypsum boards and fiber boards, adhesives for various powder granulation, additives for cement and mortar, hot melt adhesives, pressure-sensitive adhesives, and fixing agents for anionic coating materials.
(3) Coating agent: a transparent coating agent for paper, a pigment coating agent for paper, an internal sizing agent for paper, a sizing agent for fiber products, a warp sizing agent, a fiber processing agent, a leather surface finishing agent, a coating material, an antifogging agent, a metal anticorrosive agent, a brightening agent for zinc plating, an antistatic agent, a conductive agent, a temporary coating material, and the like.
(4) Suspension dispersion stabilizer: pigment dispersion stabilizers such as paints, inks, aqueous pigments, adhesives, etc.; dispersion stabilizers for suspension polymerization of various vinyl compounds such as vinyl chloride, 1-dichloroethylene, styrene, (meth) acrylic acid esters, and vinyl acetate.
(5) Emulsification dispersion stabilizer: emulsifiers for emulsion polymerization of various acrylic monomers, olefinic unsaturated compounds, and butadiene compounds; hydrophobic resins such as polyolefin and polyester resins, and post-emulsifiers such as epoxy resins, paraffin and asphalt.
(6) Thickening agent: various aqueous solutions, emulsions, thickeners for petroleum-mining fluids, and the like.
(7) Flocculating agent: flocculating agent of suspended matter and dissolved matter in water; pulp, slurry water filters, and the like.
(8) And (3) the other: soil conditioners, photosensitizers, photosensitive resist resins, and the like.
The modified polyvinyl alcohol has an average particle diameter of 50 to 1000 μm. Preferably 100 to 900 μm, and particularly preferably 150 to 750 μm. When the powder is too fine, there is a tendency that the powder is likely to form lumps upon reaction with the modifier to cause reaction unevenness; when the powder is too coarse, it also tends to react incompletely with the modifier.
Here, the average particle size is a particle size in which a sieve having openings of 1700 μm, 1000 μm, 850 μm, 500 μm, 250 μm, and 150 μm is attached to a vibration machine, raw polyvinyl alcohol particles are sieved by a sieving machine into particles having particle sizes of 1700 μm or more, 1000 μm or more and less than 1700 μm, 850 μm or more and less than 1000 μm, 500 μm or more and less than 850 μm, 250 μm or more and less than 500 μm, and 150 μm or more and less than 250 μm, and the cumulative value of the particle size distribution of the powder obtained from the respective weights is 50% by weight.
Compared with the prior art, the invention has the beneficial effects that:
the invention aims to obtain a polyvinyl alcohol product with ultrahigh polymerization degree through chemical modification, the molecular weight is increased through crosslinking, and double bonds are added on a polymer chain, so that the activity can be improved, and the application of the polyvinyl alcohol product as a reaction type auxiliary agent is facilitated, such as: the emulsion polymerization of vinyl monomers takes part in the reaction. Meanwhile, compared with the traditional polyvinyl alcohol, the structure increases the hydrophobic result after crosslinking, and is beneficial to the water resistance of the polyvinyl alcohol.
Description of the drawings:
figure 1 shows a flow diagram of the Vinyl Acetate (VAM) reaction.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
Example 1
A 1-liter 316L stainless steel reaction kettle is used, a Y-shaped filter is arranged at a discharge port, 100g of selected polyvinyl alcohol powder is added into the closed reaction kettle, the alcoholysis degree of the polyvinyl alcohol (PVA) is 95.6mole percent, the viscosity of a 4% aqueous solution at 20 ℃ is 55.0mPa.s, and the sodium acetate is 0.74 g; adding 30g of acetic acid (acetic acid) and 5g of methyl acetate, heating to 80 ℃, keeping the temperature for 75 minutes, then cooling to 55 ℃, adding 30g of monomethyl fumarate at one time, keeping the temperature at 55 ℃, and reacting for 4 hours to finish. And opening a valve of the filter, discharging unreacted liquid, closing the valve, adding 180g of methanol, washing for 20 minutes, discharging, and continuously repeating the washing and discharging processes for two times. The polyvinyl alcohol was taken out and dried in a vacuum oven at 100 ℃ for 90 minutes to obtain sample 1.
the total solid content was 98.7%;
the alcoholysis degree is 87.1 mole%;
viscosity of 4% aqueous solution at 20 ℃: 155.0 mPa.s.
Example 2
A 1-liter 316L stainless steel reaction kettle is used, a Y-shaped filter is arranged at a discharge port, 100g of selected polyvinyl alcohol powder is added into the closed reaction kettle, the alcoholysis degree of the polyvinyl alcohol (PVA) is 88.2mole percent, the viscosity of a 4 percent aqueous solution at 20 ℃ is 48.0mPa.s, and the sodium acetate is 0.56; continuously adding 45g of propionic acid, heating to 65 ℃, keeping the temperature for 60 minutes, keeping the temperature for 65 ℃, adding 35g of dibutyl maleate at one time, keeping the temperature for 65 ℃, and reacting for 190 minutes to finish the reaction. And opening a valve of the filter, discharging unreacted liquid, closing the valve, adding 150g of methyl acetate, washing for 20 minutes, discharging, and continuously repeating the washing and discharging processes for two times. The polyvinyl alcohol was taken out and dried in a vacuum oven at 90 ℃ for 120 minutes to obtain sample 2.
Sample 2 was measured using the test method of national standard polyvinyl alcohol:
the total solid content is 98.5%;
the alcoholysis degree is 82.5 mole%;
viscosity of 4% aqueous solution at 20 ℃: 99.2 mPa.s;
application example 1:
the VAE emulsion polymerization process is illustrated in FIG. 1:
viscosity results were tested using the national standard analysis method:
and (4) conclusion: the VAE emulsion made using sample 1 had about a 50% reduction in PVA usage and the emulsion made had a viscosity value about 50% higher than the emulsion made using PVA 2688.
Application example 2:
sample 2 was used as a Vinyl Acetate (VAM) reactive emulsifier and reacted according to the following feed sequence of fig. 1, with the following formulation:
the VAE emulsion polymerization process is illustrated in FIG. 1:
the viscosity results were tested by the national standard analysis method:
| domestic PVA2688 | Sample No. 2 | |
| Total solid content | 42.0％ | 42.0％ |
| Viscosity 2rpm at 30 ℃ | 42500 | 57800 |
| Viscosity at 30 ℃ 20rpm | 11000 | 23300 |
And (4) conclusion: the VAE emulsion prepared in comparative sample 2 with the domestic PVA2688 was prepared in a high solid content using the same amount of PVA, and the viscosity of the emulsion prepared in sample 2 was significantly higher than that of the emulsion prepared in PVA 2688.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (9)
1. A preparation method of modified ultra-high molecular weight polyvinyl alcohol is characterized by comprising the following steps: adding polyvinyl alcohol powder into a reaction kettle, continuously adding a certain amount of solvent as a reaction carrier, heating, stirring, adding a modifier, and washing and drying a product by using a washing solvent after the reaction is finished to obtain the modified polyvinyl alcohol with the ultrahigh molecular weight.
2. The method of claim 1, wherein the weight ratio of the polyvinyl alcohol to the modifier is 100: 12-50.
3. The method as claimed in claim 1, wherein the mass ratio of the polyvinyl alcohol, the modifier, the reaction carrier and the washing solvent is 100:12-50:15-45: 100-.
4. The method of claim 1, wherein the modifier is an enedioic acid monoester compound.
5. The method of claim 1, wherein the modifier is selected from the group consisting of: one or a mixture of monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl maleate, monoethyl maleate or monobutyl maleate.
6. The method of claim 1, wherein the reaction temperature is 30 to 90 ℃.
7. A modified polyvinyl alcohol obtained by the production method according to any one of claims 1 to 6, wherein the total solid content is: greater than 95.0%; alcoholysis degree mole% range: 75 mole% to 95 mole%; viscosity of 4% aqueous solution at 20 ℃ mPa.s: 90.0-250.0.
8. Use of the modified polyvinyl alcohol according to claim 7 for a shaped article, an adhesive, a coating agent, a suspension dispersion stabilizer, an emulsion dispersion stabilizer, a thickener, a flocculant, a soil conditioner, a photosensitizer, or a photosensitive resist resin.
9. The use of a modified polyvinyl alcohol according to claim 8, wherein the modified polyvinyl alcohol has an average particle diameter of 50 to 1000 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003670A (en) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | Use of organic base for improving formability of polyvinyl alcohol |
| CN116003668A (en) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | Preparation method of high-viscosity polyvinyl alcohol |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3582513A (en) * | 1968-02-09 | 1971-06-01 | Borden Inc | High viscosity polyvinyl alcohol from high-solids,low-viscosity conditioned polyvinyl ester solutions |
| JPH08311112A (en) * | 1995-05-19 | 1996-11-26 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer for suspension polymerization of vinyl-compound |
| CN101421309A (en) * | 2006-04-12 | 2009-04-29 | 可乐丽股份有限公司 | Dispersion stabilizer |
| CN105492471A (en) * | 2013-10-30 | 2016-04-13 | 日本合成化学工业株式会社 | Acetoacetyl-group-containing polyvinyl alcohol resin powder, and method for producing same |
| CN110234666A (en) * | 2016-12-28 | 2019-09-13 | 株式会社可乐丽 | Vinyl alcohol polymer and its manufacturing method containing pendant olefins |
| CN110330592A (en) * | 2019-07-29 | 2019-10-15 | 安徽天润化学工业股份有限公司 | A kind of preparation method for making fragrant adhesive polyacrylamide |
| US20190330396A1 (en) * | 2016-12-28 | 2019-10-31 | Kuraray Co., Ltd. | Vinyl polymer production method |
-
2019
- 2019-12-06 CN CN201911239942.4A patent/CN111072800B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3582513A (en) * | 1968-02-09 | 1971-06-01 | Borden Inc | High viscosity polyvinyl alcohol from high-solids,low-viscosity conditioned polyvinyl ester solutions |
| JPH08311112A (en) * | 1995-05-19 | 1996-11-26 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer for suspension polymerization of vinyl-compound |
| CN101421309A (en) * | 2006-04-12 | 2009-04-29 | 可乐丽股份有限公司 | Dispersion stabilizer |
| CN105492471A (en) * | 2013-10-30 | 2016-04-13 | 日本合成化学工业株式会社 | Acetoacetyl-group-containing polyvinyl alcohol resin powder, and method for producing same |
| CN110234666A (en) * | 2016-12-28 | 2019-09-13 | 株式会社可乐丽 | Vinyl alcohol polymer and its manufacturing method containing pendant olefins |
| US20190330396A1 (en) * | 2016-12-28 | 2019-10-31 | Kuraray Co., Ltd. | Vinyl polymer production method |
| CN110330592A (en) * | 2019-07-29 | 2019-10-15 | 安徽天润化学工业股份有限公司 | A kind of preparation method for making fragrant adhesive polyacrylamide |
Non-Patent Citations (7)
| Title |
|---|
| BO ZHAO: "Solvent-free esterification of poly(vinyl alcohol) and maleic", 《CHINESE CHEMICAL LETTERS》 * |
| 候少武等: "《聚乙烯醇市场、生产技术、应用》", 28 February 2017 * |
| 冯文婕等: "化学交联对改善聚乙烯醇膜耐水性的研究", 《广州化工》 * |
| 孟平蕊 等: "PVA-MA 酯化交联作用的FT-IR 研究", 《中国塑料》 * |
| 章悦庭 等: "高吸水改性聚乙烯醇（PVA）的制取及性能", 《中国纺织大学学报》 * |
| 角田隆弘等: "《印刷技术简明教程》", 31 March 1983 * |
| 邢凤兰: "印染助剂", 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003670A (en) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | Use of organic base for improving formability of polyvinyl alcohol |
| CN116003668A (en) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | Preparation method of high-viscosity polyvinyl alcohol |
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Address after: No. 106 Shunda Street, Anda Industrial Park, Dagang Economic Development Zone, Binhai New Area, Tianjin, 300000 Patentee after: Tianjin xindema Group Co.,Ltd. Address before: No. 106 Shunda Street, Anda Industrial Park, Dagang Economic Development Zone, Binhai New Area, Tianjin, 300000 Patentee before: TIANJIN SUNNYMER SUSPENDING AGENTS CO.,LTD. |
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Effective date of registration: 20230712 Address after: No. 106 Shunda Street, Anda Industrial Park, Dagang Economic Development Zone, Binhai New Area, Tianjin, 300000 Patentee after: Tianjin xindema Group Co.,Ltd. Patentee after: Sindma (Inner Mongolia) Technology Co.,Ltd. Address before: No. 106 Shunda Street, Anda Industrial Park, Dagang Economic Development Zone, Binhai New Area, Tianjin, 300000 Patentee before: Tianjin xindema Group Co.,Ltd. |