CN109879990A - A kind of method that the sour phase suspension of clean and environmental protection prepares chlorinated polypropylene - Google Patents
A kind of method that the sour phase suspension of clean and environmental protection prepares chlorinated polypropylene Download PDFInfo
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- CN109879990A CN109879990A CN201910068360.8A CN201910068360A CN109879990A CN 109879990 A CN109879990 A CN 109879990A CN 201910068360 A CN201910068360 A CN 201910068360A CN 109879990 A CN109879990 A CN 109879990A
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- chlorinated polypropylene
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Abstract
The present invention relates to the methods that a kind of sour phase suspension of clean and environmental protection prepares chlorinated polypropylene, belong to chemical technology field, specific steps are as follows: neutralization reaction, hydrochloric acid and magnesia keep constant temperature to carry out neutralization reaction in reaction unit, obtain magnesium oxide solution；De- slag is filtered, magnesium oxide solution is filtered so that filter residue is separated with magnesium chloride solution, to filter residue washing；The magnesium chloride solution filtered after taking off slag is evaporated in evaporation, and magnesium chloride solution is made to be increased to concentration greater than 46%；Sheeting, packaging, by the magnesium chloride solution contact pin after evaporation, packaging.The technique for hydrochloric acid and the magnesia reaction that the present invention uses produces magnesium chloride, and product is pure white free from foreign meter, the external circulation temperature lowering mode of use, prevents from causing to be boiling over because solution temperature increases, keeps opposite constant temperature, accelerate reaction speed, reaction is abundant.
Description
Technical field
The invention belongs to chemical technology field, the sour phase suspension for being related to a kind of clean and environmental protection prepares the side of chlorinated polypropylene
Method.
Background technique
Chlorinated polypropylene is that have the performances such as good oil resistant, heat-resisting, acid-fast alkali-proof and UV radiation, is being applied
Material, adhesive, ink vehicle and leather treatment etc. have a wide range of applications, and other field is also constantly being opened up
It is wide.
Chlorinated polypropylene (CPP) is there are mainly two types of production method, one is solvent method, besides water phase suspension.Using
Solvent method, specific embodiment are that polypropylene and carbon tetrachloride solvent are matched by a certain percentage in addition reaction kettle, are being greater than 100
Polypropylene is dissolved at a temperature of DEG C, adds a small amount of initiator, and chlorination reaction, chlorination occur under normal pressure and certain condition
Solution afterwards obtains chlorinated polypropylene through removal solvent.The advantages of solvent method is that chlorination is uniform, and product chlorination degree is up to 25%-
63%, the disadvantage is that product has remaining solvent, product quality is poor, and the loss of solvent is big in production process, and high production cost is right
Environmental pollution is serious, and foreign countries mainly take advanced water phase suspension technique production chlorinated polypropylene.Aqueous phase technique is by powdery
Reactor is added in polypropylene, softened water, emulsion and catalyst by a certain percentage, and being sufficiently stirred makes polypropylene at suspension.It stirs
Mix it is lower polypropylene suspension liquid is heated to 40 DEG C, be passed through liquid chlorine and be allowed to chlorination.Stablized during the reaction by heat exchanger and is reacted
The temperature of device.Reach certain green chlorination degree, stops logical chlorine.Chlorinated polypropylene mother liquor washs by separation, is dried to obtain water
The chlorinated polypropylene of phase method production.Aqueous phase produces chlorinated polypropylene and equipment is required to have good corrosion resistance, while generating waste water
The disadvantages of more.Because the chlorinated polypropylene wet feed after depickling washes away to form slurry depickling again by process water, the above depickling operation
2-3 times, thus there is diluted acid and acid-bearing wastewater discharge amount are big, cannot recycling and reusing, the method processing neutralized can only be used,
Treated, and waste water still has that saliferous is high, pollutes the environment.Producing 1 ton of chlorinated polypropylene water consumption is 30-
40 tons, serious waste water resource.Therefore, the preparation method of high-quality, free of contamination chlorinated polypropylene is urgently to be solved at present
Problem.
Summary of the invention
The present invention provides the method that a kind of sour phase suspension of clean and environmental protection prepares chlorinated polypropylene, present invention process letters
Organic solvent that is single, having pollution without using carbon tetrachloride etc., without discharge of wastewater, the neutralization technique of Aqueous phase, is not shortened
Process flow, it is low in cost.In addition to producing chlorinated polypropylene product, by-product hydrochloric acid is gone back.
What the present invention was realized using following technical scheme:
A kind of method that the sour phase suspension of clean and environmental protection prepares chlorinated polypropylene, specific steps are as follows:
1. hydrochloric acid is put into reactor heating；
2. polypropylene is added into hydrochloric acid, emulsifier is stirred, addition dispersing agent, initiation after making polypropylene emulsification, being swollen
Agent, anti-fouling agent；
3. being passed through liquid chlorine heat temperature raising simultaneously into reactor, reacted, continues constant temperature cooling chlorination again after reaction terminating
Polypropylene mother liquor.
4. obtained chlorinated polypropylene mother liquor is filtered, is separated, being dried to obtain chlorinated polypropylene product and by-product hydrochloric acid.
It is further preferred that in parts by weight are as follows: 60-70 parts of the polypropylene dosage, the emulsifier 0.4-
0.6 part, described dispersant dosage 1.2-1.6 parts, 0.2 part of the initiator amount, 1.5 parts of the anti-fouling agent dosage is described
500 parts of hydrochloric acid dosage.
It is further preferred that in parts by weight are as follows: 64 parts of the polypropylene dosage, 0.5 part of the emulsifier, institute
State 1.5 parts of dispersant dosage, 0.2 part of the initiator amount, 1.5 parts of the anti-fouling agent dosage, the hydrochloric acid dosage 500
Part.
It is further preferred that emulsifier used is neopelex.The raw materials used in the present invention is polypropylene powder,
And the powder compact structure, specific surface are small, it is the swelling in order to emulsify the powder that emulsifier, which is added, increases specific surface area, makes it
Increase with the contact area of liquid chlorine, to be conducive to the progress of reaction, and the selected emulsifier of the present invention be propylene oxide and
The polymer of ethylene oxide, mass fraction are 0.5 part
It is further preferred that initiator used was di-tert-butyl peroxide, the dispersing agent is the prior art in the art
?.
It is further preferred that the mass fraction of the hydrochloric acid is 16%-22%, polyacrylic c h bond can be compared at this concentration
Low, hydrogen is easy to be replaced by chlorine, reaction mechanism:
[C3H6]n+mnCl2→[C3H6-mClm]n+mnHCl
It is further preferred that the viscous kettle agent is hydrophobic silica.
It is further preferred that step (1) temperature that is heated to is 70 DEG C.
It is further preferred that 60-80 DEG C of the temperature of step (2) described emulsification swelling, time 0.5-6h.
It is further preferred that step (3) heating temperature rises to 150 DEG C by 70 DEG C, lead to when temperature rises to 150 DEG C by 70 DEG C
Enter the 50% of required liquid chlorine quality, 150 DEG C of constant temperature zones have led to remaining liquid chlorine, terminate reaction at the end of leading to chlorine.
It is further preferred that step (3) reactor pressure is less than 0.5Mpa, reaction time 4-6h.
It is further preferred that step (3) terminate reaction after continue keep 150 DEG C of temperature, the time be 5~30min so that
Chlorination reaction carries out relatively thorough.
It is further preferred that the total amount of the logical liquid chlorine is the 72%-96% of haloflex quality.
It is further preferred that it is 25-63% that step (3) haloflex obtained, which is chlorinity mass fraction,.
By-product hydrochloric acid described in step (4) is that reaction starts the preceding hydrochloric acid being added and the hydrochloric acid summation generated after reaction.It is dense
Degree is higher than the concentration before reaction, and other additives can be filtered major part after filtering, and residual volume is considerably less, and by-product hydrochloric acid can
Reach the requirement of HG/T 3783-2005 " by-product hydrochloric acid " standard.
Compared with prior art, the present invention at least has the advantages that
(1) method that the sour phase suspension of clean and environmental protection provided by the invention prepares chlorinated polypropylene, has without using carbon tetrachloride etc.
Malicious solvent, while also emitting no waste water, it is environment amenable production technology；Meanwhile carbon tetrachloride is also free of in product.
(2) method that the sour phase suspension of clean and environmental protection provided by the invention prepares chlorinated polypropylene selects polypropylene powder,
Powder compact structure, specific surface is small, and it is to emulsify the powder that emulsifier, which is added, and swelling increases specific surface area, makes itself and liquid chlorine
Contact area increases, thus be conducive to the progress of reaction,
(3)) method that the sour phase suspension of clean and environmental protection provided by the invention prepares chlorinated polypropylene, it is simple process, pollution-free, do not have
There is the neutralization technique of Aqueous phase, shortens process flow, it is low in cost, in addition to producing chlorinated polypropylene product, by-product hydrochloric acid is gone back,
It can be directly for sale.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
Present embodiments provide the method that a kind of sour phase suspension of clean and environmental protection prepares chlorinated polypropylene, specific steps are as follows:
1. 500 parts of hydrochloric acid are first added in enamel glass kettle, the mass fraction of hydrochloric acid is 16%, is added to hydrochloric acid in enamel glass kettle
Heat to 70 DEG C,
2. 64 parts of polypropylene, 0.5 part of emulsifier neopelex are added after opening the stirring of enamel glass kettle, at 60 DEG C
It is swollen 6h, adds 1.5 parts of polyethylene of dispersing agent pyrrolidones (K30), 1.5 parts of hydrophobic silicas, 0.2 part of two uncle of initiator
Butylperoxide；
3. liquid chlorine (total amount of logical liquid chlorine is the 72% of chlorinated polypropylene quality) is passed through to enamel glass kettle, when reaction temperature is by 70
Logical chlorine mass ratio is 50% when DEG C rising to 150 DEG C, and 150 DEG C of constant temperature zones have led to remaining liquid chlorine, is terminated when reaching and setting logical chlorine dose anti-
Answer, continue to keep 150 DEG C of temperature, time be 5min so that chlorination reaction carry out relatively thoroughly, total reaction time is 4 small
When, cooling makes temperature of charge be down to 65 DEG C, obtains chlorinated polypropylene hydrochloric acid suspension；
4. pair enamel glass kettle material passes through centrifuge separation, dry obtained chlorinated polypropylene and by-product hydrochloric acid.
Raw material used above and each auxiliary agent are in parts by weight.
Case study on implementation 2
A kind of preparation method of the sour phase suspension method production chlorinated polypropylene of clean and environmental protection is present embodiments provided, step is such as
Under:
1. 500 parts of hydrochloric acid (mass fraction 16%) are first added in enamel glass kettle, hydrochloric acid in enamel glass kettle is heated to
70℃；2. 60 parts of polypropylene, 0.4 part of emulsifier neopelex are added after opening the stirring of enamel glass kettle, at 60 DEG C
Emulsification swelling 6h, 1.2 dispersing agent K30,1.5 parts of anti-acidblocking agent hydrophobic silicas, 0.2 part of initiator di-tert-butyl peroxide
Object；
3. liquid chlorine (total amount of logical liquid chlorine is the 96% of chlorinated polypropylene quality) is passed through to enamel glass kettle, when reaction temperature is by 70
Logical chlorine mass ratio is 65% when DEG C rising to 150 DEG C, and 150 DEG C of constant temperature zones have led to remaining liquid chlorine, is terminated when reaching and setting logical chlorine dose anti-
Answer, continue to keep 150 DEG C of temperature, time be 5min so that chlorination reaction carry out relatively thoroughly, total reaction time is 6 small
When, cooling makes temperature of charge be down to 65 DEG C, obtains chlorinated polypropylene hydrochloric acid suspension；
4. pair reaction kettle material passes through centrifuge separation, dry obtained chlorinated polypropylene and by-product hydrochloric acid.
Raw material used above and each auxiliary agent are in parts by weight.
Present embodiments provide the method that a kind of sour phase suspension of clean and environmental protection prepares chlorinated polypropylene, specific steps are as follows:
1. 500 parts of hydrochloric acid are first added in enamel glass kettle, the mass fraction of hydrochloric acid is 22%, is added to hydrochloric acid in enamel glass kettle
Heat to 70 DEG C,
2. 70 parts of polypropylene, 0.6 part of emulsifier neopelex are added after opening the stirring of enamel glass kettle, at 70 DEG C
It is swollen 4h, adds 1.6 parts of polyethylene of dispersing agent pyrrolidones (K30), 1.5 parts of hydrophobic silicas, 0.2 part of two uncle of initiator
Butylperoxide；
3. liquid chlorine (total amount of logical liquid chlorine is the 80% of chlorinated polypropylene quality) is passed through to enamel glass kettle, when reaction temperature is by 70
Logical chlorine mass ratio is 50% when DEG C rising to 150 DEG C, and 150 DEG C of constant temperature zones have led to remaining liquid chlorine, is terminated when reaching and setting logical chlorine dose anti-
Answer, continue to keep 150 DEG C of temperature, time be 5min so that chlorination reaction carry out relatively thoroughly, total reaction time is 4 small
When, cooling makes temperature of charge be down to 65 DEG C, obtains chlorinated polypropylene hydrochloric acid suspension；
4. pair enamel glass kettle material passes through centrifuge separation, dry obtained chlorinated polypropylene and by-product hydrochloric acid.
Raw material used above and each auxiliary agent are in parts by weight.
By the embodiment 1-3 chlorinated polypropylene prepared and existing Eastman Chemical Company, the U.S., Japanese Toyo Ink into
Row performance comparison is shown in Table 1, and is tested for the property to the by-product hydrochloric acid of embodiment 1-3, is shown in Table 2.
1 chlorinated polypropylene performance test of table comparison
| Detection project | Case study on implementation 1 | Case study on implementation 2 | Case study on implementation 3 | Eastman Chemical Company, the U.S. | Japanese Toyo Ink |
| Appearance | White powder | White powder | White powder | White powder | White powder |
| Chlorinty, % | 36 | 60 | 60 | 63 | 45 |
| Viscosity, (25 ± 1 DEG C of rotational viscometer) Mpas | 280 | 320 | 320 | 300 | 280 |
| Solubility, % | 99 | 99 | 99 | 99 | 99 |
| Moisture content, % | 0.2 | 0.2 | 0.2 | 0.3 | 0.5 |
2 by-product hydrochloric acid performance test of table
As shown in Table 1, international most advanced level is had reached by technical solution provided by the invention chlorinated polypropylene produced.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. the method that a kind of sour phase suspension of clean and environmental protection prepares chlorinated polypropylene, specific steps are as follows:
(1) hydrochloric acid is put into reactor heating；
(2) polypropylene is added into hydrochloric acid, emulsifier is stirred, addition dispersing agent, initiation after making polypropylene emulsification, being swollen
Agent, anti-fouling agent；
(3) it is passed through liquid chlorine heat temperature raising simultaneously into reactor, is reacted, continues constant temperature cooling chlorination again after reaction terminating
Polypropylene mother liquor；
(4) the chlorinated polypropylene mother liquor obtained is filtered, is separated, being dried to obtain chlorinated polypropylene product and by-product hydrochloric acid.
2. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: in parts by weight are as follows: described
60-70 parts of polypropylene dosage, described emulsifier 0.4-0.6 parts, described dispersant dosage 1.2-1.6 parts, the initiator
0.2 part of dosage, 1.5 parts of the anti-fouling agent dosage, 500 parts of the hydrochloric acid dosage.
3. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: in parts by weight are as follows: described
64 parts of polypropylene dosage, 0.5 part of the emulsifier, 1.5 parts of the dispersant dosage, 0.2 part of the initiator amount, institute
1.5 parts of anti-fouling agent dosage are stated, 500 parts of the hydrochloric acid dosage.
4. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: emulsifier used is dodecyl
Benzene sulfonic acid sodium salt, initiator used are benzoyl peroxide, and the mass fraction of the hydrochloric acid is 16%-22%, and the viscous kettle agent is hydrophobic
Silica.
5. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: step (1) is described to be heated to temperature
Degree is 70 DEG C.
6. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: step (2) described emulsification swelling
60-80 DEG C of temperature, time 0.5-6h.
7. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: step (3) heating temperature is by 70
DEG C 150 DEG C are risen to, the 50% of required liquid chlorine quality is passed through when temperature rises to 150 DEG C by 70 DEG C, 150 DEG C of constant temperature zones have led to residue
Liquid chlorine terminates reaction at the end of leading to chlorine.
8. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: step (3) reactor pressure
Less than 0.5Mpa, reaction time 4-6h.
9. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: it is subsequent that step (3) terminates reaction
150 DEG C of temperature is held in continuation of insurance, the time is 5~30min.
10. the method according to claim 1 for preparing chlorinated polypropylene, it is characterised in that: the total amount of the logical liquid chlorine is
The 72% of haloflex quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449000A (en) * | 2022-09-05 | 2022-12-09 | 山东高信化学股份有限公司 | Method for preparing chlorinated polypropylene resin by aqueous phase suspension method |
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| CN105175585A (en) * | 2015-10-14 | 2015-12-23 | 奉化市裕隆化工新材料有限公司 | Method for preparing chlorinated polyethylene in acid medium |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463104A (en) * | 2008-12-27 | 2009-06-24 | 潍坊亚星集团有限公司 | Method for producing high chlorinated polyethylene |
| CN102532360A (en) * | 2011-12-27 | 2012-07-04 | 东营旭业化工有限公司 | Acid phase method production process for chlorinated polyethylene rubber |
| CN104558305A (en) * | 2014-02-24 | 2015-04-29 | 江苏中煦高分子材料有限公司 | Process for synthesizing chlorinated polyvinyl chloride by virtue of acid-phase suspension method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449000A (en) * | 2022-09-05 | 2022-12-09 | 山东高信化学股份有限公司 | Method for preparing chlorinated polypropylene resin by aqueous phase suspension method |
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Application publication date: 20190614 |