CN110407961B

CN110407961B - Preparation method of polyvinyl butyral

Info

Publication number: CN110407961B
Application number: CN201910670380.2A
Authority: CN
Inventors: 王世伟; 高立峰; 李宇; 魏奇; 于丽敏
Original assignee: Changchun University of Technology
Current assignee: Changchun University of Technology
Priority date: 2019-07-24
Filing date: 2019-07-24
Publication date: 2022-08-02
Anticipated expiration: 2039-07-24
Also published as: CN110407961A

Abstract

The invention relates to a method for preparing polyvinyl butyral (PVB) by using a novel catalyst. By using the novel catalyst which is independently developed, the problems of adhesion, caking, pipeline corrosion and the like in the PVB resin production process can be effectively reduced, and the resin production efficiency is obviously improved. The PVB resin prepared by the method has the advantages of uniform particles, uniform distribution of functional groups, high acetalization degree and high bulk density, and is very suitable for preparing PVB films for laminated glass.

Description

Preparation method of polyvinyl butyral

Technical Field

The invention relates to the technical field of a preparation method of high-performance resin, in particular to a method for preparing polyvinyl butyral by using a novel catalyst.

Background

Polyvinyl butyral (PVB) is prepared from polyvinyl alcohol (PVA) and butyraldehyde, and has good transparency, excellent chemical stability, impact resistance, low temperature resistance, light resistance and heat resistance in acid, and strong binding power to materials such as glass, metal and the like.

The existing synthesis processes of polyvinyl butyral resin are classified into a homogeneous phase method and a heterogeneous phase method. The homogeneous phase method usually uses polyvinyl acetate as a starting material, ensures that alcoholysis and acetalization reaction are carried out simultaneously in a system, and finally obtains a finished product through the steps of precipitation, washing, drying and the like. The heterogeneous method is characterized in that PVA is used as a starting material to form an aqueous solution, then n-butyraldehyde and an acid catalyst are added, PVB powder is gradually separated out through reaction at a certain temperature, and finally, washing and drying are carried out to obtain a finished product. But the homogeneous method is gradually abandoned due to the complicated process. The heterogeneous method is widely used because of its simple post-treatment method.

Hydrochloric acid or other weak acids are used as catalysts in the existing heterogeneous production process to catalyze the reaction of PVA and butyraldehyde to prepare PVB resin. However, hydrochloric acid as a catalyst has strong acidity, is not easy to control, corrodes pipelines, has low single weak acid catalytic efficiency and the like, so that the production efficiency of the high-viscosity PVB resin is low, the product performance reliability is poor and the like, and therefore, the development of a novel high-efficiency PVB synthesis composite catalyst is imperative.

Disclosure of Invention

The invention provides a method for preparing polyvinyl butyral resin, which comprises the following steps:

(1) adding PVA and deionized water of a certain mass into a reactor, starting stirring, and simultaneously heating to 90-95 ℃ until the PVA and the deionized water are dissolved.

(2) And cooling to room temperature, and adding the emulsifier.

(3) And (3) continuously cooling to 10-25 ℃, adding an acid catalyst, reacting for a period of time, adding a n-butyl aldehyde solution, and reacting for a period of time in the state to obtain the suspension of the polyvinyl butyral.

(4) Heating to 60-80 ℃ for reaction, and maintaining for a period of time. After the reaction is finished, cooling the reaction system, adding a sodium hydroxide solution, adjusting the pH value, washing and drying.

Preferably, the mass fraction of PVA in step (1) should be controlled to be 2% to 30%.

Further, the emulsifier in the step (2) is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium stearate, sodium abietate and dodecyl trimethyl ammonium bromide.

In the step (3), the acid solution is maleic acid, and the mass ratio of the maleic acid to the PVA should be controlled to be 1: (5-25). Meanwhile, the purity of the n-butyraldehyde is more than 98%, and the mass ratio of the n-butyraldehyde to the polyvinyl alcohol is controlled to be 1: (1-3).

Further, the polyvinyl butyral product obtained in the step (5) is dried at 50-60 ℃.

Further, the structural formula of the novel catalyst in the step (3) is as follows:

wherein M may be one or more of the following:

、

、

、

、

n may be one or more of the following:

、

、

、

、

、

、

、

、

r may be one of the following:

、

、

or

、

Wherein if R is an aromatic structure, the substituent comprises three positions of ortho-position, meta-position and para-position

X ranges from 0 to 10

The innovation points of the invention are as follows:

1. a series of composite acid catalysts are automatically synthesized, are specially used for synthesizing high-performance polyvinyl butyral (PVB) resin powder, effectively improve the acetalization degree of the PVB resin powder and obviously improve the utilization rate of raw materials compared with the traditional hydrochloric acid catalysis process, and are completely suitable for the application of laminated glass.

2. By utilizing the composite acid catalyst synthesized by the method, in the process of synthesizing the PVB resin powder, the qualified PVB resin powder can be obtained by directly adding the catalyst into a reaction system at one time, so that the production process is greatly simplified, and the problem of acid catalytic corrosion of metal pipelines in the conventional production process is solved.

Detailed Description

The following examples are given to facilitate a better understanding of the invention with respect to the examples, but are not meant to limit the scope of the invention. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.

Comparative example:

200g of PVA and 2L of water were put into a three-necked flask equipped with a stirrer and heated to 95 ℃ or higher to dissolve the PVA. Adding a certain amount of n-butyl aldehyde at the temperature of 40-60 ℃. And then cooling to below 15 ℃, adding hydrochloric acid, reacting for 0.5 h-1 h, slowly heating to 70-80 ℃, keeping for 1-1.5 h, cooling to below 40 ℃, filtering, mashing with a tissue mashing machine, washing with deionized water for 2 times, adjusting the pH value with NaOH solution, standing for 1h, washing for 3-4 times, and drying at 50 ℃.

Example 1

15g of PVA and 150ml of deionized water were placed in a three-necked flask equipped with a stirrer and dissolved by heating at a temperature of 95 ℃. After dissolving, cooling to room temperature, adding 10ml of SDBS, stirring uniformly, adding 0.6g of trinitropropionic acid at one time, increasing the rotating speed, stirring for 15min, adding 11.25ml of n-butyl aldehyde, reacting for 1h at the temperature, transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to room temperature, adding sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB powder is then filtered and the product is rinsed with deionized water until the filtrate is neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 1 are shown in the table below

Example 2

15g of PVA and 150ml of deionized water were placed in a three-necked flask equipped with a stirrer and dissolved by heating at a temperature of 95 ℃. After dissolving, cooling to room temperature, adding 10ml of SDBS, stirring uniformly, adding 1.5g of trinitropropionic acid at one time, increasing the rotating speed, stirring for 15min, adding 11.25ml of n-butyl aldehyde, continuously reacting for 1h at the temperature, then transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to the room temperature after the reaction is finished, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB particles were then filtered and rinsed with deionized water until the filtrate was neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 2 are given in the table below

Example 3

15g of PVA and 150ml of deionized water were placed in a three-necked flask equipped with a stirrer and dissolved by heating at a temperature of 95 ℃. Cooling to room temperature after dissolution, then adding 10ml of SDBS, stirring uniformly, then adding 0.3g of maleic acid and 0.3g of trinitropropionic acid at one time, increasing the rotating speed, stirring for 15min, then adding 11.25ml of n-butyl aldehyde, continuously reacting for 1h at the temperature, then transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to a room temperature state after the reaction is finished, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB particles were then filtered and rinsed with deionized water until the filtrate was neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 3 are given in the table below

Example 4

15g of PVA and 150ml of deionized water were placed in a three-necked flask equipped with a stirrer and dissolved by heating at a temperature of 95 ℃. Cooling to room temperature after dissolution, then adding 10 SDBS, stirring uniformly, then adding 1.0g of maleic acid and 0.5g of trinitropropionic acid at one time, increasing the rotation speed, stirring for 15min, then adding 11.25ml of n-butyl aldehyde, continuously reacting for 1h at the temperature, then transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to a room temperature state after the reaction is finished, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB particles were then filtered and rinsed with deionized water until the filtrate was neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 4 are given in the table below

Example 5

15g of PVA and 150ml of deionized water were placed in a three-necked flask equipped with a stirrer and dissolved by heating at a temperature of 95 ℃. After dissolving, cooling to room temperature, adding 10ml of SDBS, stirring uniformly, adding 0.25g of 3-nitrothiophenecarboxylic acid and 0.35g of 4-chloro-1-pentanesulfonic acid at one time, increasing the rotation speed, stirring for 15min, adding 7.5ml of n-butyraldehyde, continuously reacting for 1h at the temperature, transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to room temperature after the reaction is finished, adding a sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB particles were then filtered and rinsed with deionized water until the filtrate was neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 5 are given in the table below

Example 6

15PVA and 150ml of deionized water were added to a three-necked flask equipped with a stirrer, and heated to dissolve at a temperature of 95 ℃. After dissolving, cooling to room temperature, adding 10ml of SDBS, stirring uniformly, adding 0.5g of 3-nitrothiophenecarboxylic acid and 1.0g of 4-chloro-1-pentanesulfonic acid at one time, increasing the rotation speed, stirring for 15min, adding 7.5ml of n-butyl aldehyde, continuously reacting for 1h at the temperature, transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to room temperature after the reaction is finished, adding a sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB particles were then filtered and rinsed with deionized water until the filtrate was neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 6 are given in the table below

Example 7

15g of PVA and 150ml of deionized water were placed in a three-necked flask equipped with a stirrer and dissolved by heating at a temperature of 95 ℃. Cooling to room temperature after dissolution, then adding 7ml of SDBS, stirring uniformly, then adding 0.6g of 4-chloro-1-pentanesulfonic acid at one time, increasing the rotation speed, stirring for 15min, then adding 7.5ml of n-butyl aldehyde, continuously reacting for 1h at the temperature, then transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to the room temperature after the reaction is finished, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB particles were then filtered and rinsed with deionized water until the filtrate was neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 7 are given in the table below

Example 8

15g of PVA and 150ml of deionized water were placed in a three-necked flask equipped with a stirrer and dissolved by heating at a temperature of 95 ℃. Cooling to room temperature after dissolution, then adding 7ml of SDBS, stirring uniformly, then adding 1.0g of 4-chloro-1-pentanesulfonic acid at one time, increasing the rotation speed, stirring for 15min, then adding 11.25ml of n-butyl aldehyde, continuously reacting for 1h at the temperature, then transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to the room temperature after the reaction is finished, then adding a sodium hydroxide solution, and adjusting the pH value of the solution to be more than 7. The PVB particles were then filtered and rinsed with deionized water until the filtrate was neutral. And finally, drying the prepared product for 48 hours at the temperature of 55 ℃.

The performance indices of the polyvinyl butyrals prepared in example 8 are given in the table below

Note: the acid used in the above examples has the following structure

Claims

1. A method for preparing polyvinyl butyral resin with improved viscosity and bulk density is characterized by comprising the following steps:

adding 15g of PVA and 150ml of deionized water into a three-neck flask with a stirrer, heating for dissolving, wherein the dissolving temperature is 95 ℃, cooling to room temperature after dissolving, then adding 10ml or 7ml of SDBS, stirring uniformly, then adding a catalyst at one time, increasing the rotating speed, stirring for 15min, then adding 11.25ml of n-butyl aldehyde, continuously reacting for 1h at the temperature, then transferring into an oil bath kettle at 70 ℃, reacting for 4h, cooling to the room temperature after the reaction is finished, then adding a sodium hydroxide solution, adjusting the pH value of the solution to be more than 7, then filtering out PVB particles, washing with deionized water until the filtrate is neutral, and finally drying the prepared product for 48h at 55 ℃;

when the catalyst is maleic acid and trinitropropionic acid, the addition amount of the maleic acid is 1.0g, and the addition amount of the trinitropropionic acid is 0.5 g;

when the catalyst is 4-chloro-1-pentanesulfonic acid, the amount of the 4-chloro-1-pentanesulfonic acid added is 1.0 g.