CN105399874B - A kind of polyvinyl butyral resin synthetic method based on homogeneous and heterogeneous two-stage reaction - Google Patents
A kind of polyvinyl butyral resin synthetic method based on homogeneous and heterogeneous two-stage reaction Download PDFInfo
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- CN105399874B CN105399874B CN201510897731.5A CN201510897731A CN105399874B CN 105399874 B CN105399874 B CN 105399874B CN 201510897731 A CN201510897731 A CN 201510897731A CN 105399874 B CN105399874 B CN 105399874B
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Abstract
The present invention relates to a kind of polyvinyl butyral resin synthetic method based on homogeneous and heterogeneous two-stage reaction.Polyvinyl alcohol water solution, a small amount of n-butanal and HCl solution are sufficiently mixed first, homogeneous reaction occurs, obtains homogeneous phase solution；Then remaining n-butanal is disposably distributed in the homogeneous phase solution in droplets, obtains heterogeneous reaction system, heterogeneous reaction occurs, then heated up that the reaction was continued and completed to reaction, it is filtering, washing, dry, obtain PVB products.The present invention ensures to complete part aldolisation under homogeneous phase condition first, reduce PVA molecules hydroxyl groups density, the addition of control n-butanal makes the close critical condition for separating out solid PVB of system after reacting early period, remaining n-butanal rapid precipitation is added on this basis goes out PVB solids, obtain micrometer level porous particle, the load of heterogeneous reaction is effectively reduced with transmitting resistance, realizes the synthesis of high acetalizing degree PVB, while substantially increase n-butanal utilization rate.
Description
Technical field
The invention belongs to resins synthesis technical field, more particularly to a kind of poly- second based on homogeneous and heterogeneous two-stage reaction
Enol butyral synthetic method.
Background technology
Polyvinyl butyral resin (PVB) is used as a kind of fluoropolymer resin, is mainly used for automobile and building trade, can be used as vapour
The intermediate adhesion layer of car windshield, bulletproof glass, building coating adhesive, are the sealing material of solar cell photovoltaic substrate
Important materials in material, LED substrate manufacturing process.
High quality P VB requires acetalizing degree to reach more than 78%, i.e. the segment with acetal groups accounts for the quality of whole molecule
Fraction is higher than 78%, and hydroxyl is uniformly distributed, and to meet the translucency index of adhesive layer, is made particularly with LED substrate
Middle consumptive material, the requirement even more high of acetalizing degree.
In the precipitation method prepare PVB techniques, material polyethylene alcohol (PVA) is hydrophilic molecule, butyraldehyde as organic matter and
PVA poor compatibilities, solubility in water are low, thus exist in initial reaction stage with drops.During the reaction, butyraldehyde liquid
PVA near drop is initially formed low acetalizing degree PVB with partly soluble butyraldehyde.When acetalizing degree reaches critical value (20~30%)
When, PVB is separated out from solution, easily wraps up unreacted PVA at this time.In traditional handicraft, since butyraldehyde disposably adds instead
System is answered, initial reaction stage must be strictly controlled the conditions such as low temperature, hydrochloric acid rate of addition, while just can guarantee that using strong mixing equipment
Micron-sized PVB is formed, in order to the development of follow-up solid-liquid reaction process, this design for reaction equipment and technique proposes
Very high requirement.Once equipment or operating condition cannot be met the requirements, the PVB bulky grains of parcel PVA are easily formed in system, are led
Butyraldehyde is caused to be difficult to further go deep into solid interior completion subsequent reactions under the influence of inside diffusional resistance, so as to final acetal
Degree produces serious influence.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of polyvinyl alcohol contracting based on homogeneous and heterogeneous two-stage reaction
Butyraldehyde synthetic method.
A kind of polyvinyl butyral resin synthetic method based on homogeneous and heterogeneous two-stage reaction, comprises the following steps：
(1) part n-butanal is added into PVA aqueous solutions at 5~35 DEG C, and adds HCl solution, is sufficiently mixed, is carried out
Homogeneous reaction, reaction duration are no less than 30min, obtain homogeneous phase solution；Wherein the mass ratio of n-butanal and PVA is less than 0.15:1,
The mass ratio of HCl and PVA is (0.02~0.5):1；
(2) remaining n-butanal is disposably distributed in droplets in step (1) described homogeneous phase solution, makes positive fourth
The total addition of aldehyde and the mass ratio of PVA additions are (0.5~1.0):1, reaction temperature is maintained, makes it under heterogeneous conditions
React 0.5~4h；50~65 DEG C are then raised temperature to, the reaction was continued 1~8h is completed to reacting, and is finally cooled to 25~45 DEG C, is obtained
To PVB slurries；
(3) PVB slurries filtered, washed, is dry, obtaining PVB products.
The mass fraction of PVA is less than 15% in PVA aqueous solutions in step (1), and the mass fraction of HCl is less than in HCl solution
37.5%.
The particle diameter of drop is within 500 μm described in step (2).
Consersion unit is stirred tank, high-speed emulsifying machine or micro-structured reactor used by reaction, and combinations thereof.
Beneficial effects of the present invention are：The addition of present invention control first stage n-butanal, guarantee system is in homogeneous bar
First stage reaction is completed under part, system is close to the critical condition for separating out solid PVB after making reaction, and the solution after reaction is in homogeneous
State, the homogeneous phase solution without solid, the reaction of this first stage reduce the hydroxy density in solution in PVA molecules, improve PVA
The lipophile of molecule, and this PVA molecules with a small amount of acetal radical effectively reduce the load of late phase reaction, are conducive to add
Fast second stage adds the course of dissolution of n-butanal.The reaction solution that homogeneous phase solution to close on set point is reacted as second stage,
Remaining n-butanal is rapidly joined under strong dispersion condition, most hemiacetal reactions and part are completed before PVB precipitation generations
Aldolisation, is conducive to the high acetalizing degree and its uniformity of product；PVB particles are made to sink rapidly by the high degree of supersaturation of system
Form sediment, according to the basic principle of crystallography, this coprecipitation mode is advantageous to form a large amount of micron particles, the micron order of acquisition
Porous particle effectively reduces the load of second stage heterogeneous reaction with transmitting resistance, thus ensure that subsequent reactions it is smooth into
OK, the rapid conversion of the n-butanal under heterogeneous conditions is realized；Micron particles are further completed final under Elevated Temperature Conditions
Aldolisation, so as to obtain the PVB products of high acetalizing degree.
The present invention is used is with heterogeneous two-stage reaction PVB synthetic methods, the acetalizing degree of products obtained therefrom PVB based on homogeneous
78~82%, hydroxyl value (vinyl alcohol groups account for the mass fraction of whole molecule) is controllable in the range of 16~20%, is divided equally with number
The PVA of son amount 75000 ± 5000 is the PVB of Material synthesis, and the viscosity of its 5% ethanol solution is 60~115mPas, Neng Gouman
The production requirement of a variety of diaphragms such as sufficient automotive grade, architectural grade and binding agent.The present invention is while product PVB high acetalizing degrees are ensured
Butyraldehyde utilization rate is substantially increased, has saved Material Cost and subsequent wash cost.
Embodiment
With reference to embodiment, the present invention will be further described.It is emphasized that the description below is only
Exemplary, the scope being not intended to be limiting of the invention and its application.
Following embodiments carry out in stirred tank, other chemical production devices also can be used in application process.
A kind of polyvinyl butyral resin synthetic method based on homogeneous and heterogeneous two-stage reaction, includes the following steps：
(1) PVA aqueous solutions are prepared, add part n-butanal, and add HCl solution, is sufficiently mixed, occurs under homogeneous phase condition
Reaction, obtains homogeneous phase solution；
(2) remaining n-butanal is disposably distributed in droplets in step (1) described homogeneous phase solution, non-equal
Reacted under the conditions of phase, then the reaction was continued to reaction completion for heating, obtains PVB slurries；
(3) conventional filtration, washing, drying are carried out to PVB slurries, obtains PVB products.
The viscosity of sampling analysis its acetalizing degree, hydroxyl value and 5% ethanol solution.
Embodiment 1
Reaction condition：The mass fraction of PVA is 5% in PVA aqueous solutions；A small amount of n-butanal and HCl solution is added to be formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.06:The mass ratio of 1, HCl and PVA is 0.15:1, in HCl solution
The mass fraction of HCl is 10%；The reaction temperature of homogeneous reaction is 35 DEG C, time 50min；After remaining n-butanal adds,
The mass ratio of heterogeneous reaction progress 1.5h, n-butanal total amount and initial p VA in reaction solution are 0.65:1；It is anti-at 65 DEG C again
Should at a temperature of, the reaction was continued 3.0h；Finally it is cooled to 35 DEG C.
Reaction result：The acetalizing degree of product PVB is 79.1%, hydroxyl value 18.3%, and the viscosity of 5%PVB ethanol solutions is
89mPa·s。
Embodiment 2
Reaction condition：The mass fraction of PVA is 15% in PVA aqueous solutions；A small amount of n-butanal and HCl solution is added to be formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.10:The mass ratio of 1, HCl and PVA is 0.10:1；In HCl solution
The mass fraction of HCl is 10.0%；The reaction temperature of homogeneous reaction is 30 DEG C, time 90min；Remaining n-butanal adds it
Afterwards, the mass ratio of heterogeneous reaction progress 0.5h, n-butanal total amount and initial p VA in reaction solution are 0.64:1；Again at 65 DEG C
Reaction temperature under, the reaction was continued 2.0h；Finally it is cooled to 30 DEG C.
Reaction result：The acetalizing degree of product PVB is 78.6%, hydroxyl value 19.3%, and the viscosity of 5%PVB ethanol solutions is
80mPa·s。
Embodiment 3
Reaction condition：The mass fraction of PVA is 10% in PVA aqueous solutions；A small amount of n-butanal and HCl solution is added to be formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.10:The mass ratio of 1, HCl and PVA is 0.11:1；In HCl solution
The mass fraction of HCl is 7.5%；The reaction temperature of homogeneous reaction is 25 DEG C, time 65min；After remaining n-butanal adds,
The mass ratio of heterogeneous reaction progress 1.25h, n-butanal total amount and initial p VA in reaction solution are 0.82:1；Again at 70 DEG C
Under reaction temperature, the reaction was continued 1.0h.Finally it is cooled to 45 DEG C.
Reaction result：The acetalizing degree of product PVB is 79.2%, hydroxyl value 18.8%, and the viscosity of 5%PVB ethanol solutions is
87mPa·s。
Embodiment 4
Reaction condition：The mass fraction of PVA is 11% in PVA aqueous solutions；A small amount of n-butanal and HCl solution is added to be formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.08:The mass ratio of 1, HCl and PVA is 0.08:1；In HCl solution
The mass fraction of HCl is 18.5%；The reaction temperature of homogeneous reaction is 37 DEG C, time 100min；Remaining n-butanal adds it
Afterwards, the mass ratio of heterogeneous reaction progress 2.5h, n-butanal total amount and initial p VA in reaction solution are 0.73:1；Again at 62 DEG C
Reaction temperature under, the reaction was continued 5.5h.Finally it is cooled to 42 DEG C.
Reaction result：The acetalizing degree of product PVB is 81.0%, hydroxyl value 17.6%, and the viscosity of 5%PVB ethanol solutions is
105mPa·s。
Embodiment 5
Reaction condition：The mass fraction of PVA is 6% in PVA aqueous solutions；A small amount of n-butanal and HCl solution is added to be formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.06:The mass ratio of 1, HCl and PVA is 0.08:1；In HCl solution
The mass fraction of HCl is 25%；The reaction temperature of homogeneous reaction is 15 DEG C, time 30min；After remaining n-butanal adds,
The mass ratio of heterogeneous reaction progress 3.0h, n-butanal total amount and initial p VA in reaction solution are 0.56:1；It is anti-at 55 DEG C again
Should at a temperature of, the reaction was continued 3.0h.Finally it is cooled to 40 DEG C.
Reaction result：The acetalizing degree of product PVB is 78.6%, hydroxyl value 19.1%, and the viscosity of 5%PVB ethanol solutions is
78mPa·s。
Embodiment 6
Reaction condition：The mass fraction of PVA is 10% in PVA aqueous solutions；A small amount of n-butanal and HCl solution is added to be formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.12:The mass ratio of 1, HCl and PVA is 0.06:1；In HCl solution
The mass fraction of HCl is 16%；The reaction temperature of homogeneous reaction is 30 DEG C, time 150min；After remaining n-butanal adds,
The mass ratio of heterogeneous reaction progress 1.0h, n-butanal total amount and initial p VA in reaction solution are 0.66:1；It is anti-at 53 DEG C again
Should at a temperature of, the reaction was continued 8.0h.Finally it is cooled to 30 DEG C.
Reaction result：The acetalizing degree of product PVB is 78.0%, hydroxyl value 19.7%, and the viscosity of 5%PVB ethanol solutions is
68mPa·s。
Embodiment 7
Reaction condition：The mass fraction of PVA is 14% in PVA aqueous solutions, adds a small amount of n-butanal and HCl solution and is formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.15:The mass ratio of 1, HCl and PVA is 0.21:1；In HCl solution
The mass fraction of HCl is 35%；The reaction temperature of homogeneous reaction is 36 DEG C, time 60min；After remaining n-butanal adds,
The mass ratio of heterogeneous reaction progress 4.0h, n-butanal total amount and initial p VA in reaction solution are 0.72:1；It is anti-at 65 DEG C again
Should at a temperature of, the reaction was continued 2.0h.Finally it is cooled to 25 DEG C.
Reaction result：The acetalizing degree of product PVB is 81.5%, hydroxyl value 17.0%, and the viscosity of 5%PVB ethanol solutions is
107mPa·s。
Embodiment 8
Reaction condition：The mass fraction of PVA is 10% in PVA aqueous solutions；A small amount of n-butanal and HCl solution is added to be formed
Solution is mixed, the wherein mass ratio of n-butanal and PVA is 0.10:The mass ratio of 1, HCl and PVA is 0.12:1；In HCl solution
The mass fraction of HCl is 25%；The reaction temperature of homogeneous reaction is 22 DEG C, time 140min；After remaining n-butanal adds,
The mass ratio of heterogeneous reaction progress 2.0h, n-butanal total amount and initial p VA in reaction solution are 0.80:1；It is anti-at 60 DEG C again
Should at a temperature of, the reaction was continued 3.5h.Finally it is cooled to 33 DEG C.
Reaction result：The acetalizing degree of product PVB is 82.0%, hydroxyl value 16.7%, and the viscosity of 5%PVB ethanol solutions is
112mPa·s。
Claims (4)
- A kind of 1. polyvinyl butyral resin synthetic method based on homogeneous and heterogeneous two-stage reaction, it is characterised in that this method Comprise the following steps：(1) part n-butanal is added into PVA aqueous solutions at 5~35 DEG C, and adds HCl solution, is sufficiently mixed, is carried out homogeneous Reaction, reaction duration are no less than 30min, obtain homogeneous phase solution；Wherein the mass ratio of n-butanal and PVA is less than 0.15:1, HCl with The mass ratio of PVA is (0.02~0.5):1；(2) remaining n-butanal is disposably distributed in droplets in step (1) described homogeneous phase solution, makes n-butanal total The mass ratio of addition and PVA additions is (0.5~1.0):1, reaction temperature is maintained, it is reacted under heterogeneous conditions 0.5~4h；50~65 DEG C are then raised temperature to, the reaction was continued 1~8h is completed to reacting, and is finally cooled to 25~45 DEG C, is obtained PVB Slurries；(3) PVB slurries filtered, washed, is dry, obtaining PVB products.
- A kind of 2. synthetic method according to claim 1, it is characterised in that in step (1) in PVA aqueous solutions PVA quality Fraction is less than 15%, and the mass fraction of HCl is less than 37.5% in HCl solution.
- 3. a kind of synthetic method according to claim 1, it is characterised in that the particle diameter of drop is at 500 μm described in step (2) Within.
- A kind of 4. synthetic method according to claim 1, it is characterised in that used by reaction consersion unit for stirred tank, High-speed emulsifying machine or micro-structured reactor, and combinations thereof.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690379A (en) * | 2012-06-18 | 2012-09-26 | 四川宝利丰科技有限公司 | Method for preparing polyvinyl butyral high-polymer resin |
| 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 |
| CN103193905A (en) * | 2013-04-03 | 2013-07-10 | 东莞市龙怡阻燃材料有限公司 | Low-viscosity polyvinyl butyral resin as well as preparation method and application thereof |
| CN105001359A (en) * | 2015-07-21 | 2015-10-28 | 上海应用技术学院 | Polyvinyl butyral preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690379A (en) * | 2012-06-18 | 2012-09-26 | 四川宝利丰科技有限公司 | Method for preparing polyvinyl butyral high-polymer resin |
| CN103193905A (en) * | 2013-04-03 | 2013-07-10 | 东莞市龙怡阻燃材料有限公司 | Low-viscosity polyvinyl butyral resin as well as preparation 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 |
| CN105001359A (en) * | 2015-07-21 | 2015-10-28 | 上海应用技术学院 | Polyvinyl butyral preparation method |
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