CN108440693B - High-melt-index resin and preparation method thereof - Google Patents
High-melt-index resin and preparation method thereof Download PDFInfo
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- CN108440693B CN108440693B CN201810353324.1A CN201810353324A CN108440693B CN 108440693 B CN108440693 B CN 108440693B CN 201810353324 A CN201810353324 A CN 201810353324A CN 108440693 B CN108440693 B CN 108440693B
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- pva1792
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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
- C08F8/28—Condensation with aldehydes or ketones
Abstract
The invention discloses a high-melt-index resin and a preparation method thereof, wherein the high-melt-index resin comprises PVA1792, PVA2099, n-butyraldehyde and hydrochloric acid, the mass ratio of the PVA1792 to the PVA2099 is 1:2.3-4.1, the mass ratio of a mixture of the PVA1792 and the PVA2099 to the n-butyraldehyde is 1:0.3-0.5, and the use amount of the hydrochloric acid is based on the mass final concentration of the hydrochloric acid in an aqueous solution of the PVA mixture and the n-butyraldehyde being 0.8-1.0%. The PVA with low alcoholysis degree and the PVA with high polymerization degree are mixed and fed without changing other process parameters, so that the PVB with higher viscosity and the same high melt index is produced.
Description
Technical Field
The invention relates to a production process of a high molecular polymer, in particular to a high-melt-index resin and a preparation method thereof.
Background
Polyvinyl Butyral (PVB). Is the product of polyvinyl alcohol (PVA) and butyraldehyde in acid catalysis.
In recent years, with the rapid development of the automobile and building industries, a very good development opportunity is provided for PVB intermediate film manufacturers. The high-end PVB in China is imported totally, the main reason is that the production process and matched raw materials are insufficient, and the PVB production process is characterized in that a PVA (polyvinyl alcohol) aqueous solution reacts with butyraldehyde under the action of a catalyst to generate polyvinyl butyral resin, and the polyvinyl butyral resin is washed by water and dried to form PVB powder resin. Compared with foreign production technology, the equipment and the technology of the invention seriously lags behind the same foreign production technology. And the traditional old process technology is adopted in China, and production enterprises do not have matched PVB film research institutions, which is also the reason that PVB for high-end films is imported completely.
High-viscosity PVB resin is a direction of technical development at present, which can not only improve the mechanical properties of a PVB film, but also improve the weather resistance and stability of a film, but the high viscosity is accompanied by the increase of polymerization degree, which leads to the reduction of melt index, which causes great difficulty to the manufacturing and processing of the film, and also influences the reduction of indexes of the film such as optical properties and the like. Increasing the melt index of high viscosity PVB resins is a very important condition for improving film quality. The PVA model used in the traditional PVB resin production process is basically 1799, the polymerization degree is about 1700, and the traditional method for increasing the melt index comprises the following steps: 1. raising the reaction temperature; 2. increasing the amount of catalyst acid; 3. the material feeding amount of PVA is reduced, and the like.
Although the method 1 can obviously improve the melt index, the material is easy to agglomerate at high reaction temperature, and the weather resistance is also reduced.
The method 2 adds the catalyst, thereby not only improving the cost, but also increasing the burden on the subsequent sewage treatment.
Method 3 substantially reduces the content of hydroxyl groups in the resin powder, which greatly affects the adhesive properties of the film.
Increasing the melt index on an original basis has been a difficult point, and if resin powders with higher viscosity are to be developed, the requirement for the melt index is difficult.
Disclosure of Invention
Aiming at the technical problems, the invention provides the high-melt-index resin and the preparation method thereof, and the PVB with higher viscosity and the same high melt index is produced by mixing the PVA with low alcoholysis degree and the PVA with high polymerization degree without changing other process parameters.
The resin with the high melt index comprises PVA1792, PVA2099, n-butyraldehyde and hydrochloric acid, wherein the mass ratio of the PVA1792 to the PVA2099 is 1:2.3-4.1, the mass ratio of a mixture of the PVA1792 and the PVA2099 to the n-butyraldehyde is 1:0.3-0.5, and the use amount of the hydrochloric acid is based on the mass final concentration of the hydrochloric acid in an aqueous solution of the PVA mixture and the n-butyraldehyde being 0.8-1.0%.
Preferably, the mass ratio of the PVA1792 to the PVA2099 is 1: 3-3.4.
Preferably, the mass ratio of the mixture of PVA1792 and PVA2099 to the n-butyraldehyde is 1: 0.5.
The invention provides another technical scheme that the preparation method of the high-melt-index resin comprises the following steps:
(1) mixing PVA1792 and PVA2099 according to the mass ratio of 1:2.3-4.1, and then dissolving the PVA mixture in water to obtain a PVA aqueous solution;
(2) mixing the PVA mixture and n-butyl aldehyde according to the mass ratio of 1:0.3-0.5, adding the n-butyl aldehyde into the PVA aqueous solution, and stirring uniformly;
(3) adding a hydrochloric acid solution into the solution in the step (2) until the mass final concentration of hydrochloric acid is 0.8-1.0%, then reacting for 5h at 24 ℃, and then respectively preserving heat for 1h at 35 ℃, 45 ℃ and 55 ℃;
(4) and (4) centrifuging the reaction product obtained in the step (3), taking the precipitate, washing, neutralizing and drying the precipitate to obtain the PVB with high melt index.
The melt index of the resin powder depends on many factors, and the proportion of the groups in the molecule largely determines the melt index under the same raw material and the same process.
After the condensation reaction of PVA and butyraldehyde, the molecule of the generated PVB contains three groups, and the typical PVB resin has the following structural formula:
the A group is easy to form intermolecular hydrogen bond, which is an important factor influencing the melt index, and the content of the A group in the PVA with low alcoholysis degree is reduced, so that the proportion of the A group in the PVB resin powder is reduced, and the melt index is increased under the condition of not changing other indexes.
Compared with the prior art, the method has the following positive effects: the traditional process usually changes process parameters on the aspect of improving the index of the resin powder, one index is improved, the other index is reduced, and the quality improvement in the real sense is not realized.
The present invention will be further described with reference to the following examples.
Detailed Description
Example one
The high melt index resin of example one, prepared by the following method:
(1) mixing 50kg of PVA1792 with 115kg of PVA2099, and then dissolving the PVA mixture in water to obtain a PVA aqueous solution with the mass fraction of 8%;
(2) adding 49.5kg of n-butyraldehyde to the PVA aqueous solution, and uniformly stirring;
(3) adding a hydrochloric acid solution into the solution in the step (2) until the mass final concentration of hydrochloric acid is 0.8%, then reacting for 5h at 24 ℃, and then respectively preserving heat for 1h at 35 ℃, 45 ℃ and 55 ℃;
(4) and (4) centrifuging the reaction product obtained in the step (3), taking the precipitate, washing, neutralizing and drying the precipitate to obtain the PVB with high melt index.
The high melt index resin of example one has a melt index of 14.5g/10min at 140 ℃ under a load of 2.16kg and a viscosity of 27 mPas (test Standard GB/T12010.2-2010).
Example two
The high melt index resin of example two was prepared by the following method:
(1) mixing 50kg of PVA1792 with 150kg of PVA2099, and then dissolving the PVA mixture in water to obtain a PVA aqueous solution with the mass fraction of 9%;
(2) adding 100kg of n-butyraldehyde to the PVA aqueous solution, and uniformly stirring;
(3) adding a hydrochloric acid solution into the solution in the step (2) until the mass final concentration of hydrochloric acid is 1.0%, then reacting for 5h at 24 ℃, and then respectively preserving heat for 1h at 35 ℃, 45 ℃ and 55 ℃;
(4) and (4) centrifuging the reaction product obtained in the step (3), taking the precipitate, washing, neutralizing and drying the precipitate to obtain the PVB with high melt index.
The high melt index resin of example two had a melt index of 19.5g/10min at 140 ℃ under a load of 2.16kg and a viscosity of 28 mPas (test Standard GB/T12010.2-2010).
EXAMPLE III
The high melt index resin of example three was prepared by the following method:
(1) mixing 50kg of PVA1792 with 170kg of PVA2099, and then dissolving the PVA mixture in water to obtain a PVA water solution with the mass fraction of 10%;
(2) adding 88kg of n-butyraldehyde to the PVA aqueous solution, and uniformly stirring;
(3) adding a hydrochloric acid solution into the solution in the step (2) until the mass final concentration of hydrochloric acid is 0.9%, then reacting for 5h at 24 ℃, and then respectively preserving heat for 1h at 35 ℃, 45 ℃ and 55 ℃;
(4) and (4) centrifuging the reaction product obtained in the step (3), taking the precipitate, washing, neutralizing and drying the precipitate to obtain the PVB with high melt index.
The high melt index resin of example three had a melt index of 20.3g/10min at a temperature of 140 ℃ under a load of 2.16kg and a viscosity of 24 mPas (test Standard GB/T12010.2-2010).
Example four
The high melt index resin of example four, prepared by the following method:
(1) mixing 20kg of PVA1792 with 82kg of PVA2099, and then dissolving the PVA mixture in water to obtain a PVA aqueous solution with the mass fraction of 10%;
(2) adding 51kg of n-butyraldehyde to the PVA aqueous solution, and uniformly stirring;
(3) adding a hydrochloric acid solution into the solution in the step (2) until the mass final concentration of hydrochloric acid is 0.9%, then reacting for 5h at 24 ℃, and then respectively preserving heat for 1h at 35 ℃, 45 ℃ and 55 ℃;
(4) and (4) centrifuging the reaction product obtained in the step (3), taking the precipitate, washing, neutralizing and drying the precipitate to obtain the PVB with high melt index.
The high melt index resin of example four had a melt index of 25.2g/10min at a temperature of 140 ℃ under a load of 2.16kg and a viscosity of 32 mPas (test Standard GB/T12010.2-2010).
The present invention is not limited to the above-described embodiments, and various changes and modifications of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.
Claims (6)
1. A high melt index resin characterized by:
the high-melt-index resin is prepared by dissolving a PVA mixture in water, adding n-butyl aldehyde into the PVA aqueous solution for mixing, adding hydrochloric acid into the mixed solution of the PVA aqueous solution and the n-butyl aldehyde, reacting for 5 hours at 24 ℃, then respectively preserving heat for 1 hour at 35 ℃, 45 ℃ and 55 ℃, and taking out the precipitate;
the PVA mixture comprises PVA1792 and PVA2099, the mass ratio of the PVA1792 to the PVA2099 is 1:2.3-4.1, the mass ratio of the mixture of the PVA1792 and the PVA2099 to n-butyraldehyde is 1:0.3-0.5, and the dosage of the hydrochloric acid is based on the mass final concentration of the hydrochloric acid in the aqueous solution of the PVA mixture and the n-butyraldehyde being 0.8-1.0%.
2. The high melt index resin of claim 1, wherein: the mass ratio of the PVA1792 to the PVA2099 is 1: 3-3.4.
3. The high melt index resin of claim 1, wherein: the mass ratio of the mixture of PVA1792 and PVA2099 to n-butyraldehyde is 1: 0.5.
4. A preparation method of high-melt-index resin is characterized by comprising the following steps:
(1) mixing PVA1792 and PVA2099 according to the mass ratio of 1:2.3-4.1, and then dissolving the PVA mixture in water to obtain a PVA aqueous solution;
(2) mixing the PVA mixture and n-butyl aldehyde according to the mass ratio of 1:0.3-0.5, adding the n-butyl aldehyde into the PVA aqueous solution, and stirring uniformly;
(3) adding a hydrochloric acid solution into the solution in the step (2) until the mass final concentration of hydrochloric acid is 0.8-1.0%, then reacting for 5h at 24 ℃, and then respectively preserving heat for 1h at 35 ℃, 45 ℃ and 55 ℃;
(4) and (4) centrifuging the reaction product obtained in the step (3), taking the precipitate, washing, neutralizing and drying the precipitate to obtain the PVB with high viscosity and high melt index.
5. The method for preparing a high melt index resin according to claim 4, wherein: the mass ratio of the PVA1792 to the PVA2099 is 1: 3-3.4.
6. The method for preparing a high melt index resin according to claim 4, wherein: the mass ratio of the mixture of PVA1792 and PVA2099 to n-butyraldehyde is 1: 0.5.
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Citations (5)
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|---|---|---|---|---|
| JPS57164178A (en) * | 1981-04-01 | 1982-10-08 | Denki Kagaku Kogyo Kk | Preparation of adhesive |
| CN102120785A (en) * | 2009-12-18 | 2011-07-13 | 可乐丽欧洲有限责任公司 | Polyvinylacetal with high flowing capability and film containing softeners produced using same |
| CN102702397A (en) * | 2012-05-14 | 2012-10-03 | 怀集县集美新材料有限公司 | Polyvinyl butyral with high impact resistance, synthetic method and application thereof |
| CN103172769A (en) * | 2013-04-24 | 2013-06-26 | 隆回群丰生物化工有限公司 | Preparation method of high-viscosity ultra-high molecular weight polyvinyl butyral resin |
| CN106496378A (en) * | 2016-10-19 | 2017-03-15 | 安徽皖维高新材料股份有限公司 | A kind of short screw extruder polyvinyl butyral resin and its production method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57164178A (en) * | 1981-04-01 | 1982-10-08 | Denki Kagaku Kogyo Kk | Preparation of adhesive |
| CN102120785A (en) * | 2009-12-18 | 2011-07-13 | 可乐丽欧洲有限责任公司 | Polyvinylacetal with high flowing capability and film containing softeners produced using same |
| CN102702397A (en) * | 2012-05-14 | 2012-10-03 | 怀集县集美新材料有限公司 | Polyvinyl butyral with high impact resistance, synthetic method and application thereof |
| CN103172769A (en) * | 2013-04-24 | 2013-06-26 | 隆回群丰生物化工有限公司 | Preparation method of high-viscosity ultra-high molecular weight polyvinyl butyral resin |
| CN106496378A (en) * | 2016-10-19 | 2017-03-15 | 安徽皖维高新材料股份有限公司 | A kind of short screw extruder polyvinyl butyral resin and its production method |
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