Emulsification polymerisation of polyvinyl acetate

(1) Monomer
The monomer is vinyl acetate, also known as vinyl acetate (VAC), the structural formula is
CH3C0OCH=CH2
Emulsion polymerization is the same as free radical addition polymerization.
It requires very high monomer purity.
(2) Emulsifier : The reaction generally uses two non-ionic emulsifiers, namely nonylphenol polyoxyethylene
ether (OP-10) and polyvinyl alcohol
(3) Initiator : Persulfates, such as ammonium persulfate and potassium persulfate can be used as initiators
(4) Other additives :
Plasticizer: dibutyl phthalate Preservatives: sodium nitrite, sodium benzoate
Defoamer: octanol
Dispersant : methanol
Antifreeze : Glycol
(5) Water
Use deionized water, because tap water contains metal ions, which can inhibit the polymerization reaction.

If tap water is used as a raw material,ethylenediaminetetraacetic acid EDTA must be added as a integrator
The initiation reaction of emulsion polymerization takes place in the micelles, and the polymerization reaction
is mainly carried out in the micelles after the initiation and the polymer particles formed therefrom.
The monomer droplets mainly play the role of monomer storage
Because the number of micelles is very large, almost only one free radical can be contained in a micelle, so the
chain termination speed is significantly reduced, resulting in a faster emulsion polymerization rate and a high
molecular weight of the obtained polymer Vinyl acetate emulsion polymerization is a type of free radical
polymerization.
It follows the general law of free radical polymerization and needs to go through three main stages: chain
initiation, chain growth, and chain termination
The mechanism of the polymerization reaction is described below
(1) Chain initiation of polymerization reaction
The monomer, water, emulsifier, initiator and other materials are added to the reactor and stirred to form an
emulsion
Vinyl acetate emulsion polymerization usually uses persulfate as the initiator, such as potassium persulfate or
ammonium persulfate.
(2) Chain growth of polymerization reaction

The monomer free radicals are combined with the monomers to initiate polymerization to form chain free
radicals, and the consumed monomers are continuously replenished by the monomer droplets through the
water phase diffused into the micelles, and so on, the monomer molecules are initiated to start the
polymerization reaction.
The polymer chain continues to grow, thereby obtaining high molecular weight polymers
.As the initiator continues to decompose, the initiation reactions in the micelles continue to occur, and the
number of active particles increases rapidly.
At this time, the chain termination rate is still relatively small, so the overall polymerization reaction rate is on
the rise
The polymerization reaction proceeds at a constant rate, and at the same time, the surface tension of the water
phase increases significantly
When the monomer conversion rate reaches 60%-70%, the monomer droplets gradually become smaller and
all disappear

(3) Chain termination of polymerization reaction

At this time, the monomer droplets no longer exist, and the remaining monomer is present in the polymer
particles and is adsorbed or swollen by the polymer
3 Synthetic process of polyvinyl acetate emulsion
(1) Reaction temperature
The reaction temperature is 75-85°C, and the reaction temperature affects the polymerization rate and the
average molecular weight of the emulsion
.
Increasing the reaction temperature speeds up the generation of free radicals.
The monomer activity increases, the chain growth rate constant increases, and thus the polymerization reaction
rate increases
.
As the reaction temperature rises.
The decomposition rate constant of the initiator increases.
When the concentration of the initiator is constant, the generation rate of free radicals increases, which causes
the chain termination rate in the latex to increase, and the average relative molecular weight of the emulsion
decreases
.
Increasing the reaction temperature will also increase the number of latex particles.
The average diameter decreases; the reaction temperature increases, causing collisions between the latex
particles, increasing the coalescence rate, and the thinning of the hydration layer on the surface of the latex
particles, which will cause the stability of the emulsion to decrease
.
If the reaction temperature is equal to or higher than the cloud point of the emulsifier, the emulsifier loses its
stabilizing effect, causing demulsification
(2) Response time
The reaction time is 8-9h
.
The reaction time is also an important factor affecting the quality of polyvinyl acetate emulsion
.
The reaction time is mainly reflected in the length of the vinyl acetate dripping time.
The longer the vinyl acetate dripping time, the smaller the emulsion particles, the more uniform the particle
size, the greater the strength of the emulsion, the better the stability, the better the transparency of the film, and
the better the water resistance.
Improve
.

(3) Feeding method

Even with the same emulsion polymerization formula.
Due to the different methods of operation, resulting in an emulsion particle size distribution, and other aspects
of molecular weight sizes not differ
.
There are three feeding methods as follows
.

①One-time addition method

All the components are added into the reactor at the same time for polymerization
.
Since vinyl monomers have a greater thermal effect during polymerization, and the emulsion polymerization
reaction speed is faster, for industrial-scale devices, this feeding method brings greater difficulties to
temperature control.
Therefore, this method is only used when the water and oil are relatively large
.
Sometimes in order to control the rate of heat release to maintain a certain polymerization temperature, the
initiator is added in batches
.
The one-time addition method is less used in actual production
②Monomer dropping method
That is, the monomer is slowly and continuously added to the aqueous solution of the emulsifier, and the
aqueous solution of the initiator is often dropped at the same time, and the temperature of the polymerization
reaction is controlled at the rate of dropping
.
Since this method is convenient to operate and easy to control the polymerization reaction, it is widely used
.

③Emulsion dripping method

That is, the materials are mixed in advance to form an emulsion, and then gradually added dropwise to the
reaction system for polymerization
.
The polymerization temperature is relatively easy to control, but this method requires pre-emulsification.
Generally, under the conditions of the emulsion polymerization formula, the monomer emulsion has poor
stability and is easy to layer.
Therefore, pre-emulsification equipment must be equipped, which increases equipment investment And power
consumption, so it is rarely used
.

(4) Synthetic operation method of polyvinyl acetate emulsion

The preparation of polyvinyl acetate emulsion can be synthesized by chemical method and short irradiation
method.
The particle size of the emulsion prepared by irradiation method is not uniform and requires high equipment,
so this method is generally not used.
Only the chemical method is introduced here
.
The chemical method has two modes: batch operation and continuous operation.
The specific preparation process is introduced below
Continuous emulsion polymerization
a.
Put an amount of deionized water and polyvinyl alcohol (PVA) into the dissolving kettle, pass steam into the
jacket of the dissolving kettle, raise the temperature to 80~85℃, stir and dissolve for 4~6h, so that the PVA is
completely dissolved.
Into 10% (mass) PVA solution
.b.
After filtering the prepared 10% (mass) PVA solution, put it into the polymerization kettle together with OP-
10
.
Start the stirring to fully mix, and then put the vinyl acetate (about 1/7 of the total amount) and 10% (mass)
potassium persulfate solution (about 2/5 of the total amount) in the metering tank into the polymerization
kettle.
, Stir and emulsify for 30min
.
c.
Pour steam into the jacket of the polymerization kettle, raise the temperature of the materials in the kettle to
60-65°C, and stop heating
.
At this time, the polymerization reaction starts.
Because it is an exothermic reaction, the temperature in the kettle automatically rises to 75~85°C.
At this time, reflux will appear in the reflux condenser.
When the reflux is reduced, start to drip into the polymerizer through the metering tank.
Add vinyl acetate, and drip potassium persulfate solution through the metering tank [add 4% to 5% (mass) of
potassium persulfate per hour]
.
Control the dripping rate to keep the polymerization temperature at 78~80℃, and the dripping is completed in
about 8 hours
.

d.
After the monomer has been added, add all the remaining potassium persulfate solution to terminate the
reaction chain
.
After all the materials have been added, the temperature will automatically rise to 90~95 ℃ and keep for
30min
.

e.
Pour cold water into the jacket of the polymerizer to cool the product to 50°C, add the specified amount of
sodium bicarbonate solution and DBP and other additives through the metering tank, stir thoroughly to make it
evenly mixed, and discharge after filtering
.
Batch emulsion polymerization

a.
Add PVA and water to the dissolving kettle and raise the temperature to 80~85℃.
Stir and dissolve for 2h, and prepare a 10% (mass) PvA solution
.
b.
After filtering the PVA aqueous solution, put it into the polymerization kettle, add OP-10 and the primer
monomer vinyl acetate, close the feeding hole, and open the cooling water
.
The temperature is raised to about 65°C within 30mm.
When liquid drops appear in the sight glass, the heating is stopped and the temperature can rise to 75-85°C by
itself
.

c.
When the reflux is normal, start to add vinyl acetate monomer dropwise
.
Add 4% to 5% ammonium persulfate every hour, and control the uniform polymerization by adjusting the
addition rate
.
The reaction temperature is controlled at 75-80°C, which can be adjusted by the amount of monomer added
.

d.
After the monomer is added, add the remaining ammonium persulfate, the temperature of the liquid material
rises to 90~95°C by itself, and the temperature is kept for 30 minutes
.
Cool to below 50°C and add 10% sodium bicarbonate solution
.

10 examples of formulations of polyvinyl acetate emulsion adhesives

(1) Monomer
The monomer is vinyl acetate, also known as vinyl acetate (VAC), the structural formula is CH3C0OCH=CH2
Emulsion polymerization is the same as free radical addition polymerization.

It requires very high monomer purity.

(2) Emulsifier
The reaction generally uses two non-ionic emulsifiers, namely nonylphenol polyoxyethylene ether (OP-10) and
polyvinyl alcohol

(3) Initiator
Persulfates, such as ammonium persulfate and potassium persulfate can be used as initiators
(4) Other additives
Plasticizer dibutyl phthalate
Preservatives sodium nitrite, sodium benzoate
Defoamer octanol
Dispersant methanol
Antifreeze Glycol
(5) Water
Use deionized water, because tap water contains metal ions, which can inhibit the polymerization reaction.
If tap water is used as a raw material, ethylenediaminetetraacetic acid must be added as a integrator

The initiation reaction of emulsion polymerization takes place in the micelles, and the polymerization reaction
is mainly carried out in the micelles after the initiation and the polymer particles formed therefrom.
The monomer droplets mainly play the role of monomer storage
.
Because the number of micelles is very large, almost only one free radical can be contained in a micelle, so the
chain termination speed is significantly reduced, resulting in a faster emulsion polymerization rate and a high
molecular weight of the obtained polymer
.
Vinyl acetate emulsion polymerization is a type of free radical polymerization.
It follows the general law of free radical polymerization and needs to go through three main stages: chain
initiation, chain growth, and chain termination
.
The mechanism of the polymerization reaction is described below
.
(1) Chain initiation of polymerization reaction
The monomer, water, emulsifier, initiator and other materials are added to the reactor and stirred to form an
emulsion
Vinyl acetate emulsion polymerization usually uses persulfate as the initiator, such as potassium persulfate or
ammonium persulfate.
(2) Chain growth of polymerization reaction
The monomer free radicals are combined with the monomers to initiate polymerization to form chain free
radicals, and the consumed monomers are continuously replenished by the monomer droplets through the
water phase diffused into the micelles, and so on, the monomer molecules are initiated to start the
polymerization reaction.
The polymer chain continues to grow, thereby obtaining high molecular weight polymers
As the initiator continues to decompose, the initiation reactions in the micelles continue to occur, and the
number of active particles increases rapidly.
At this time, the chain termination rate is still relatively small, so the overall polymerization reaction rate is on
the rise

The polymerization reaction proceeds at a constant rate, and at the same time, the surface tension of the
water phase increases significantly
.
When the monomer conversion rate reaches 60%-70%, the monomer droplets gradually become smaller and
all disappear
.

(3) Chain termination of polymerization reaction

At this time, the monomer droplets no longer exist, and the remaining monomer is present in the polymer
particles and is adsorbed or swollen by the polymer
.
3 Synthetic process of polyvinyl acetate emulsion
(1) Reaction temperature
The reaction temperature is 75-85°C, and the reaction temperature affects the polymerization rate and the
average molecular weight of the emulsion
.
Increasing the reaction temperature speeds up the generation of free radicals.
The monomer activity increases, the chain growth rate constant increases, and thus the polymerization reaction
rate increases
.
As the reaction temperature rises.
The decomposition rate constant of the initiator increases.
When the concentration of the initiator is constant, the generation rate of free radicals increases, which causes
the chain termination rate in the latex to increase, and the average relative molecular weight of the emulsion
decreases
.
Increasing the reaction temperature will also increase the number of latex particles.
The average diameter decreases; the reaction temperature increases, causing collisions between the latex
particles, increasing the coalescence rate, and the thinning of the hydration layer on the surface of the latex
particles, which will cause the stability of the emulsion to decrease
.
If the reaction temperature is equal to or higher than the cloud point of the emulsifier, the emulsifier loses its
stabilizing effect, causing demulsification
.

(2) Response time

The reaction time is 8-9h
.
The reaction time is also an important factor affecting the quality of polyvinyl acetate emulsion
.
The reaction time is mainly reflected in the length of the vinyl acetate dripping time.
The longer the vinyl acetate dripping time, the smaller the emulsion particles, the more uniform the particle
size, the greater the strength of the emulsion, the better the stability, the better the transparency of the film, and
the better the water resistance.
Improve
.

(3) Feeding method

Even with the same emulsion polymerization formula.
Due to the different methods of operation, resulting in an emulsion particle size distribution, and other aspects
of molecular weight sizes not differ
.
There are three feeding methods as follows

①One-time addition method

All the components are added into the reactor at the same time for polymerization
.
Since vinyl monomers have a greater thermal effect during polymerization, and the emulsion polymerization
reaction speed is faster, for industrial-scale devices, this feeding method brings greater difficulties to
temperature control.
Therefore, this method is only used when the water and oil are relatively large
.
Sometimes in order to control the rate of heat release to maintain a certain polymerization temperature, the
initiator is added in batches
.
The one-time addition method is less used in actual production
.
②Monomer dropping method
That is, the monomer is slowly and continuously added to the aqueous solution of the emulsifier, and the
aqueous solution of the initiator is often dropped at the same time, and the temperature of the polymerization
reaction is controlled at the rate of dropping
.
Since this method is convenient to operate and easy to control the polymerization reaction, it is widely used
.

③Emulsion dripping method

That is, the materials are mixed in advance to form an emulsion, and then gradually added dropwise to the
reaction system for polymerization
.
The polymerization temperature is relatively easy to control, but this method requires pre-emulsification.
Generally, under the conditions of the emulsion polymerization formula, the monomer emulsion has poor
stability and is easy to layer.
Therefore, pre-emulsification equipment must be equipped, which increases equipment investment And power
consumption, so it is rarely used
.

(4) Synthetic operation method of polyvinyl acetate emulsion

The preparation of polyvinyl acetate emulsion can be synthesized by chemical method and short irradiation
method.
The particle size of the emulsion prepared by irradiation method is not uniform and requires high equipment,
so this method is generally not used.
Only the chemical method is introduced here
.
The chemical method has two modes: batch operation and continuous operation.
The specific preparation process is introduced below
.
Continuous emulsion polymerization
a.
Put an amount of deionized water and polyvinyl alcohol (PVA) into the dissolving kettle, pass steam into the
jacket of the dissolving kettle, raise the temperature to 80~85℃, stir and dissolve for 4~6h, so that the PVA is
completely dissolved.
Into 10% (mass) PVA solution
.
b.
After filtering the prepared 10% (mass) PVA solution, put it into the polymerization kettle together with OP-
10 ( Octyl phenol ethoxilate-10moles) emulsifier.
.
Start the stirring to fully mix, and then put the vinyl acetate (about 1/7 of the total amount) and 10% (mass)
potassium persulfate solution (about 2/5 of the total amount) in the metering tank into the polymerization
kettle.
, Stir and emulsify for 30min
.

c.
Pour steam into the jacket of the polymerization kettle, raise the temperature of the materials in the kettle to
60-65°C, and stop heating
.
At this time, the polymerization reaction starts.
Because it is an exothermic reaction, the temperature in the kettle automatically rises to 75~85°C.
At this time, reflux will appear in the reflux condenser.
When the reflux is reduced, start to drip into the polymerizer through the metering tank.
Add vinyl acetate, and drip potassium persulfate solution through the metering tank [add 4% to 5% (mass) of
potassium persulfate per hour]
.
Control the dripping rate to keep the polymerization temperature at 78~80℃, and the dripping is completed in
about 8 hours
.

d.
After the monomer has been added, add all the remaining potassium persulfate solution to terminate the
reaction chain
.
After all the materials have been added, the temperature will automatically rise to 90~95 ℃ and keep for
30min
.

e.
Pour cold water into the jacket of the polymerizer to cool the product to 50°C, add the specified amount of
sodium bicarbonate solution and DBP and other additives through the metering tank, stir thoroughly to make it
evenly mixed, and discharge after filtering

02
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Batch emulsion polymerization

a.
Add PVA and water to the dissolving kettle and raise the temperature to 80~85℃.
Stir and dissolve for 2h, and prepare a 10% (mass) PvA solution
.
b.
After filtering the PVA aqueous solution, put it into the polymerization kettle, add OP-10 and the primer
monomer vinyl acetate, close the feeding hole, and open the cooling water
.
The temperature is raised to about 65°C within 30mm.
When liquid drops appear in the sight glass, the heating is stopped and the temperature can rise to 75-85°C by
itself
.

c.
When the reflux is normal, start to add vinyl acetate monomer dropwise
.
Add 4% to 5% ammonium persulfate every hour, and control the uniform polymerization by adjusting the
addition rate
.
The reaction temperature is controlled at 75-80°C, which can be adjusted by the amount of monomer added
.

d.
After the monomer is added, add the remaining ammonium persulfate, the temperature of the liquid material
rises to 90~95°C by itself, and the temperature is kept for 30 minutes
.
Cool to below 50°C and add 10% sodium bicarbonate solution
.

4 Formulation example of polyvinyl acetate emulsion adhesive

[Recipe] 1
Component Mass parts

Vinyl acetate 100

5.
Polyvinyl alcohol 1788
4

1.
OP-10
1
 10.
Dibutyl phthalate
9

0.
Potassium persulfate
2

0.
Sodium bicarbonate
3

Deionized water 100

Uses: Synthesize polyvinyl acetate emulsion

.
It can be used for wood, paper, packaging and construction
.

[Recipe] 2
Component Mass parts

Vinyl acetate 355

31.
Polyvinyl alcohol
5

OP-10 4

0.
Ammonium persulfate
72

1.
Sodium bicarbonate
1

Dibutyl phthalate 4

water 318

Uses: Synthesize polyvinyl acetate emulsion

.
It can be used for wood, paper, packaging and construction
.

[Recipe] 3
Component Mass parts

Polyvinyl acetate emulsion 40~100

cement 100

Fine sand 100

Calcium chloride 1

water Right amount

Uses: Used for bonding concrete and repairing docks

.

[Recipe] 4
Component Mass parts

Vinyl acetate 50

Polyvinyl alcohol 1788 and 1799 8

0.
OP-10
6

0.
Ammonium persulfate
1

Sodium bicarbonate Right amount

12.
Dibutyl phthalate
5

0.
Octanol
3

Ethylene glycol 1

0.
Aluminum Nitrate
4

water 65

Uses: Synthesize polyvinyl acetate emulsion

.
It can be used for wood, paper, packaging and construction
.
[Recipe] 5

Component Mass parts

Vinyl acetate 100

0.
Sodium Oleate 1~0.
5

0.
hydrogen peroxide 5~1.
5

water 100~120

Uses: for wood, paper, packaging and the like

.

[Recipe] 6

Component Mass parts

Vinyl acetate (initial charge) 150

Vinyl acetate (total) 1047

5% (mass) polyvinyl alcohol solution 1047

3.
Hydrogen peroxide [40% (mass)]
3

1.
Methanol
04

Uses: for wood, paper, packaging and the like

.

[Recipe] 7
Component Mass parts

Polyvinyl acetate emulsion 55

Polyvinyl alcohol 1799 3

Trichloroethylene 9

5.
Dibutyl phthalate
5

0.
preservative
3

0.
Defoamer
2

Uses: can be used for wood, paper, packaging and construction, etc.
Recipe] 8
Component Mass parts

Polyvinyl acetate emulsion 31

Polyvinyl alcohol 1799 5

Clay 10

3.
Dibutyl phthalate
5

water 50

0.
preservative
5

0.
Defoamer
2

Uses: can be used for wood, paper, packaging and construction, etc.

[Recipe] 9
Component Mass parts

Polyvinyl acetate emulsion 97

3.
Dibutyl phthalate 0~7.
0

Uses: can be used for wood, paper, packaging and construction, etc.

[Recipe] 10
Component Mass parts
Vinyl acetate 44

Polyvinyl alcohol 1788 4

0.
Ethanol
2

Ammonium persulfate Right amount

Dibutyl phthalate 6

water 55