CN110407961A - A kind of preparation method of polyvinyl butyral - Google Patents
A kind of preparation method of polyvinyl butyral Download PDFInfo
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- CN110407961A CN110407961A CN201910670380.2A CN201910670380A CN110407961A CN 110407961 A CN110407961 A CN 110407961A CN 201910670380 A CN201910670380 A CN 201910670380A CN 110407961 A CN110407961 A CN 110407961A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to a kind of methods for preparing polyvinyl butyral (PVB) using new catalyst.By using the new catalyst of this independent development, it can effectively reduce the bonding in PVB resin production technology, agglomeration, corrode the problems such as pipeline, hence it is evident that improve production of resins efficiency.The PVB resin prepared using this method, particle is uniform, functional group is evenly distributed, acetalizing degree is high, heap density is big, is very suitable to the preparation of doubling glass PVB film.
Description
Technical field
The present invention relates to a kind of technical fields of high performance resin preparation method, and in particular to a kind of to utilize new catalyst
The method for preparing polyvinyl butyral.
Background technique
Polyvinyl butyral, abbreviation PVB are that have good transparency, excellent in acid by polyvinyl alcohol (PVA) and butyraldehyde
It is different chemical stability, impact resistance, low temperature resistant, fast light, heat-resisting, while having to materials such as glass, metals extremely strong viscous
Tie power.
The existing synthesis technology of polyvinyl butyral resin is divided into homogeneous method and two kinds of multi-phases process.Homogeneous method is usually
Using polyvinyl acetate as starting material, guarantee that alcoholysis and acetalation carry out simultaneously in system, finally by precipitating, wash
It washs, drying and other steps obtain finished product.Heterogeneous rule is to form aqueous solution by starting material of PVA, and n-butanal and acid is then added
Property catalyst, at a certain temperature gradually reaction be precipitated PVB powder end, finally wash, drying finished product can be obtained.But due to equal
Phase method complex process, so by gradually abandoning.And multi-phases process is then because post-processing approach is simple so being widely used.
Catalyst is made using hydrochloric acid or other weak acid in existing multi-phases process production process, PVA is catalyzed and butyraldehyde is anti-
It answers, PVB resin is made.But hydrochloric acid is strong as acidity of catalyst, is difficult to control, corrosion pipeline, single weak acid catalytic efficiency is low
Etc. factors, keep the production efficiency of high viscosity PVB resin low, therefore properties of product poor reliability etc. is developed a kind of new and effective
It is imperative that PVB synthesizes composite catalyst.
Summary of the invention
The invention proposes a kind of methods for preparing polyvinyl butyral resin, include the following steps:
(1) PVA of certain mass and deionized water are added in reactor, open stirring, while being warming up to 90~95 DEG C, directly
To dissolution.
(2) emulsifier is added when being cooled to room temperature.
(3) when continued down is to 10~25 DEG C, acid catalyst is added, after reacting a period of time, n-butanal solution, dimension is added
It holds this state response for a period of time, obtains the suspension of polyvinyl butyral.
(4) 60~80 DEG C of reactions are warming up to, and maintain a period of time.After the reaction was completed, make reaction system cooling, be added
Sodium hydroxide solution adjusts pH value, then using going washing, dry.
Preferably, the mass fraction of PVA should be controlled 2%~30% in step (1).
Further, emulsifier described in step (2) is neopelex, dodecyl sodium sulfate, dodecane
One of base sodium sulphate, odium stearate, sodium abietate, dodecyl trimethyl ammonium bromide are a variety of.
Acid solution described in step (3) is maleic acid, and the mass ratio of maleic acid and PVA should be controlled in 1:(5~25).Together
When n-butanal purity be greater than 98%, the mass ratio of n-butanal and polyvinyl alcohol should be controlled in 1:(1~3).
Further, the polyvinyl butyral products finally obtained in step (5) should dry at 50~60 DEG C.
Further, the skeleton symbol of new catalyst described in step (3) is as follows:
Wherein M can be following one or more:、、、、
N can be following one or more:、、、、、、、、
R can be following one of which:、、Or、
If wherein R is aromatic structure, substituent group includes three ortho position, meta position, contraposition positions
The range of X is from 0~10
The innovation of the invention consists in that:
1. independently a series of complex acid catalysts have been synthesized, dedicated for high-performance polyethylene butyral (PVB) resin-oatmeal
Synthesis, compared with traditional hydrochloric acid catalysis technique, effectively improves the acetalizing degree of PVB resin powder, hence it is evident that improves raw material utilization
Rate, the application of entirely appropriate doubling glass.
2., can be by disposable straight during synthesizing PVB resin powder using the complex acid catalyst of this hair synthesis
Connecing addition reaction system can be obtained qualified PVB resin powder, enormously simplifies production technology, solves in existing production technology
The problem of acid catalysis corrosion metal tubes.
Specific embodiment
Example given below is convenient for everybody for embodiment, and the present invention has a better understanding, but this is not offered as
It is limiting the scope of the invention.Based on the embodiments of the present invention, those skilled in the art institute obtained
There are other embodiments, shall fall within the protection scope of the present invention.
Comparative example:
In the there-necked flask equipped with blender, 200gPVA and 2L water is added, is heated to 95 DEG C or more, makes it dissolve.Temperature is 40
At~60 DEG C, a certain amount of n-butanal is added.Then 15 DEG C are cooled to hereinafter, hydrochloric acid is added, reaction 0.5h~1h. is then slow
Be warming up to 70~80 DEG C, and keep 1~1.5h. etc. and be cooled to 40 DEG C hereinafter, filtering, then smashed to pieces with tissue mashing machine, spend from
Sub- water rinses 2 times, then adjusts pH value with NaOH solution, stands 1h, then rinse 3~4 times, is put at 50 DEG C dry.
Embodiment 1
15gPVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature 95
℃.It is cooled to room temperature after dissolution, 10ml SDBS is then added and is added at one time 0.6g trinitro- propionic acid after mixing evenly,
Revolving speed is improved, 15min is stirred, 11.25ml n-butanal is then added, sustained response 1h, is then transferred to 70 DEG C at this temperature
In oil bath pan, sustained response 4h. after completion of the reaction, is cooled to room temperature state, and sodium hydroxide solution is then added, and adjusts pH value of solution
Value is greater than 7.Then PVB powder end is filtered out, rinses product with deionized water, until neutrality is presented in filtrate.It is last obtained
Product dries 48h under the conditions of 55 DEG C.
The performance indicator of the polyvinyl butyral prepared in embodiment 1 such as following table
Embodiment 2
15g PVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature is
95℃.It is cooled to room temperature after dissolution, 10ml SDBS is then added and is added at one time 1.5g trinitro- third after mixing evenly
Acid improves revolving speed, stirs 15min, 11.25ml n-butanal is then added, sustained response 1h, is then transferred to 70 DEG C at this temperature
Oil bath pan in, reaction 4h. after completion of the reaction, is cooled to room temperature state, is then added sodium hydroxide solution, adjusts solution ph
Greater than 7.Then PVB particle is filtered out, is rinsed with deionized water, until neutrality is presented in filtrate.Last obtained product in
48h is dried under the conditions of 55 DEG C.
The performance indicator of the polyvinyl butyral prepared in embodiment 2 such as following table
Embodiment 3
15g PVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature is
95℃.It is cooled to room temperature after dissolution, 10ml SDBS is then added and is added at one time 0.3g maleic acid after mixing evenly
With 0.3g trinitro- propionic acid, revolving speed is improved, stirs 15min, 11.25ml n-butanal is then added, at this temperature sustained response
Then 1h is transferred in 70 DEG C of oil bath pan, reaction 4h. after completion of the reaction, is cooled to room temperature state, sodium hydroxide is then added
Solution adjusts solution ph and is greater than 7.Then PVB particle is filtered out, is rinsed with deionized water, until neutrality is presented in filtrate.
Last product obtained dries 48h under the conditions of 55 DEG C.
The performance indicator of the polyvinyl butyral prepared in embodiment 3 such as following table
Embodiment 4
15gPVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature 95
℃.Dissolution after be cooled to room temperature, 10 SDBS are then added, after mixing evenly, be added at one time 1.0g maleic acid and
0.5g trinitro- propionic acid improves revolving speed, stirs 15min, 11.25ml n-butanal is then added, at this temperature sustained response 1h
, then it is transferred in 70 DEG C of oil bath pan, reaction 4h. after completion of the reaction, is cooled to room temperature state, and it is molten that sodium hydroxide is then added
Liquid adjusts solution ph and is greater than 7.Then PVB particle is filtered out, is rinsed with deionized water, until neutrality is presented in filtrate.Most
Product obtained dries 48h under the conditions of 55 DEG C afterwards.
The performance indicator of the polyvinyl butyral prepared in embodiment 4 such as following table
Embodiment 5
15gPVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature 95
℃.It is cooled to room temperature after dissolution, 10ml SDBS is then added and is added at one time 0.25g3- nitrobenzene sulphur after mixing evenly
For carboxylic acid and chloro- penta sulfonic acid of 1- of 0.35g4-, revolving speed is improved, stirs 15min, 7.5ml n-butanal is then added, at this temperature
Then sustained response 1h is transferred in 70 DEG C of oil bath pan, reaction 4h. after completion of the reaction, is cooled to room temperature state, is then added
Sodium hydroxide solution adjusts solution ph and is greater than 7.Then PVB particle is filtered out, is rinsed with deionized water, until filtrate is presented
Neutrality.Last product obtained dries 48h under the conditions of 55 DEG C.
The performance indicator of the polyvinyl butyral prepared in embodiment 5 such as following table
Embodiment 6
15PVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature 95
℃.It is cooled to room temperature after dissolution, 10ml SDBS is then added, it is thio to be added at one time 0.5g3- nitrobenzene after mixing evenly
Carboxylic acid and chloro- penta sulfonic acid of 1- of 1.0g4- improve revolving speed, stir 15min, and 7.5ml n-butanal is then added, holds at this temperature
Continuous reaction 1h, is then transferred in 70 DEG C of oil bath pan, and reaction 4h. after completion of the reaction, is cooled to room temperature state, hydrogen is then added
Sodium hydroxide solution adjusts solution ph and is greater than 7.Then PVB particle is filtered out, is rinsed with deionized water, until in filtrate presentation
Property.Last product obtained dries 48h under the conditions of 55 DEG C.
The performance indicator of the polyvinyl butyral prepared in embodiment 6 such as following table
Embodiment 7
15gPVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature 95
℃.It is cooled to room temperature after dissolution, 7ml SDBS is then added and is added at one time chloro- penta sulphur of 1- of 0.6g4- after mixing evenly
Acid improves revolving speed, stirs 15min, 7.5ml n-butanal is then added, sustained response 1h, is then transferred to 70 DEG C at this temperature
Oil bath pan in, reaction 4h. after completion of the reaction, is cooled to room temperature state, is then added sodium hydroxide solution, adjusts solution ph
Greater than 7.Then PVB particle is filtered out, is rinsed with deionized water, until neutrality is presented in filtrate.Last obtained product in
48h is dried under the conditions of 55 DEG C.
The performance indicator of the polyvinyl butyral prepared in embodiment 7 such as following table
Embodiment 8
15gPVA and 150ml deionized water is added in the there-necked flask equipped with blender, is dissolved by heating, solution temperature 95
℃.It is cooled to room temperature after dissolution, 7ml SDBS is then added and is added at one time chloro- penta sulphur of 1- of 1.0g4- after mixing evenly
Acid improves revolving speed, stirs 15min, 11.25ml n-butanal is then added, sustained response 1h, is then transferred to 70 at this temperature
DEG C oil bath pan in, reaction 4h. after completion of the reaction, is cooled to room temperature state, is then added sodium hydroxide solution, adjusts pH value of solution
Value is greater than 7.Then PVB particle is filtered out, is rinsed with deionized water, until neutrality is presented in filtrate.Last product obtained
48h is dried under the conditions of 55 DEG C.
The performance indicator of the polyvinyl butyral prepared in embodiment 8 such as following table
Note: the sour skeleton symbol used in above-described embodiment is as follows
Claims (8)
1. a kind of preparation method of polyvinyl butyral resin, which comprises the steps of:
The polyvinyl alcohol (PVA) and deionized water of certain mass are added in reactor, stirring and dissolving under certain temperature.
2. being cooled to room temperature, emulsifier is added under stirring condition, continues to stir 30min.
3. under stirring condition, novel composite catalyst is added in the above system, after reacting a period of time, it is molten that n-butanal is added dropwise
Liquid continues to be stirred to react a period of time, obtains the suspension of polyvinyl butyral after butyraldehyde is added completely into.
After 4. system is warming up to 60~80 DEG C of reaction a period of times, sodium hydroxide solution is added in cooling down, adjust pH value to
Then neutrality makes to be washed with deionized, is drying to obtain PVB resin powder.
5. synthetic method according to claim 1, which is characterized in that the mass ratio of PVA and water can be 1 in step (1):
(3~50).
6. synthetic method according to claim 1, which is characterized in that emulsifier described in step (2) is detergent alkylate
Sodium sulfonate, dodecyl sodium sulfate, lauryl sodium sulfate, odium stearate, sodium abietate, in dodecyl trimethyl ammonium bromide
One or more mixing.
7. synthetic method according to claim 1, which is characterized in that the mass ratio of new catalyst and PVA in step (3)
It can be 1:(5~25)；The mass ratio of n-butanal and polyvinyl alcohol should be controlled in 1:(1~3).
8. the skeleton symbol of synthetic method according to claim 1, new catalyst described in step (3) is as follows:
Wherein M can be following one or more:、、、、
N can be following one or more:、、、、、、、、
R can be following one of which:、、Or、
If wherein R is aromatic structure, substituent group includes three ortho position, meta position, contraposition positions, and the range of X is from 0~10.
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Cited By (1)
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| CN111690083A (en) * | 2020-07-28 | 2020-09-22 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl butyral resin |
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