CN110256612A - A kind of preparation method of chliorinated polyvinyl chloride - Google Patents
A kind of preparation method of chliorinated polyvinyl chloride Download PDFInfo
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- CN110256612A CN110256612A CN201910614160.8A CN201910614160A CN110256612A CN 110256612 A CN110256612 A CN 110256612A CN 201910614160 A CN201910614160 A CN 201910614160A CN 110256612 A CN110256612 A CN 110256612A
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- polyvinyl chloride
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- chlorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
Abstract
The present invention provides a kind of preparation method of chliorinated polyvinyl chloride, the preparation method, comprising the following steps: prepares aaerosol solution, chlorination reaction；The chlorination reaction, including first stage chlorination, second stage chlorination；The dry powder flow of CPVC resin prepared by the present invention is 15-25s, elasticity modulus 2654-2816MPa, and rigidity is high, tensile strength 52-58MPa, simple beam impact strength 17-22kJ/m2；Excellent combination property；The present invention is added without initiator, reduces influence of the initiator residual to combinations color and lustre and thermal stability；The simultaneous reactions time is short, and the chlorination reaction time is 125-150min.Chlorination process concentration of hydrochloric acid is increased to 22% or more, and purification process reduces impurity, can be recycled, and redundance can be sold, and directly applies to metal metallurgy smelting, and the comprehensive utilization of hydrochloric acid, environmental protection, energy conservation are realized in organic synthesis and the production of calcium chloride etc..
Description
Technical field
The present invention provides a kind of preparation method of chliorinated polyvinyl chloride, belongs to chliorinated polyvinyl chloride preparation technical field.
Background technique
PVC obtains CPVC resin, its physical mechanical property, corrosion-resistant, deformation resistant and fire-retardant suppression after chlorination modified
Smoke performance etc. improves a lot, especially the raising of heat resistance, makes the application extension of CPVC to high-performance field, heat-resisting
It is applied in water pipe, pressure-resistant, corrosion resistant industrial pipeline and the high fire main of flame-retardancy requirements, has embodied apparent advantage.
Currently, chliorinated polyvinyl chloride production mainly uses water phase suspension, this method generates low concentration dilute hydrochloric acid, exploitation value
It is worth low, processing difficulty is big, is not environment-protective process.CN105461833A discloses chlorinated polyvinyl chloride resin acid phase process production work
Prepared suspension is warming up to 70 DEG C -80 DEG C, initiator is added by skill, carries out chlorination reaction, and 110 DEG C of reaction temperature.The party
The reaction temperature of method is high, and aggravation is inclined in the decomposition of product.CN104558305B discloses sour phase suspension method chliorinated polyvinyl chloride and closes
Mutually it is reaction medium with acid at technique, polyvinyl chloride, dispersant A, dispersant B and initiator is added, slowly heating emulsification to 80
DEG C, the chlorination reaction since 85 DEG C.In order to guarantee going on smoothly for reaction, initiator joined, polyvinyl chloride and initiator
Ratio is 10:0.015, and the photo and thermal stability that thus will cause PVC reduces, and can also generate unfavorable shadow to the quality of final products
It rings, but is added without initiator, will cause that reaction speed is slow, and the reaction time is long.
Existing acid phase process synthesizes CPVC, existing deficiency are as follows:
(1) to guarantee that reacts carries out addition initiator, the residual of initiator can reduce the photo and thermal stability of PVC, can also reduce
The thermal stability and service life of final products, are added without initiator, then reaction speed is slow, and the reaction time is long；
(2) under sour phase system, reaction process product is easy to reunite, agglomerates；The dry powder flow of the CPVC resin of preparation is poor；
(3) product rigidity decline is made, non-deformability decline is unfavorable for the installation and use of product.
Summary of the invention
To solve above-mentioned technical problem, the present invention provides a kind of preparation method of chliorinated polyvinyl chloride, realizes following invention
Purpose:
(1) in chlorination process, it is added without initiator, reduces influence of the initiator residual to product quality；Shorten reaction simultaneously
Time；
(2) it prevents the product of reaction process from reuniting and agglomerating, improves the free mobility of CPVC resin；
(3) elasticity modulus for improving product, enhances rigidity and non-deformability.
In order to solve the above technical problems, the present invention takes following technical scheme:
A kind of preparation method of chliorinated polyvinyl chloride, the preparation method, comprising the following steps: it is anti-to prepare aaerosol solution, chlorination
It answers；The chlorination reaction, including first stage chlorination, second stage chlorination.
It is described to prepare aaerosol solution, in chlorination tank, hydrochloric acid solution is added, polyvinyl chloride resin, dispersing agent, antitack agent, stirring is
It is even, aaerosol solution is made.By weight, the dosage of dispersing agent used is the 0.02%-1.0%, preferably 0.1- of polyvinyl chloride resin
0.8%, the dosage of anti-adhesion agent is the 0.08%-1.6%, preferably 0.4-1.5% of polyvinyl chloride resin；(polyvinyl chloride resin is molten with hydrochloric acid for solid-to-liquid ratio
The weight ratio of liquid) it is 1:3-1:9.
The concentration of hydrochloric acid solution is 16%-21%(weight ratio).
The polymerization scope of the polyvinyl chloride resin is 500-2500, and the range of choice of optimization is 650-1500, more preferably
Range of choice is 650-1300；Average particle size range is 160 μm -230 μm, and optimum choice is 180 μm -210 μm；Apparent density
0.55g/ml-0.65g/ml。
The height of the degree of polymerization indicates the size of polyvinyl chloride resin molecular weight, is the principal element for influencing properties of product.Of PVC
Granularity and apparent density influence the load factor and load of chlorination reaction, and have an impact to the granularity of CPVC resin.Particle
Carefully, dispersion difficulty is big, and product is easy to reunite and agglomerates, and the dry powder flow of CPVC is bad, and particle is thick, and chlorination is uneven, product matter
Amount decline.
The dispersing agent is being total to for neopelex, sodium polymethacrylate, ethylene oxide and propylene oxide
One or two kinds of combinations of polymers, polyvinylpyrrolidone, polyether surfactant；
The anti-adhesion agent is one of talcum powder, silica, silicone oil；
The chlorination reaction is evacuated to -0.06 ~ -0.08MPa, removes oxygen in kettle.Steam valve heating is opened, while being opened logical
Chlorine valve is passed through chlorine, sets the initial temperature of reaction as 40 DEG C -50 DEG C, reaction terminating temperature is 80 DEG C -100 DEG C, preferably 81-
95 DEG C, pressure 0.3-0.4MPa is set, the weight ratio for leading to chlorine dose and polyvinyl chloride resin is 0.4-0.9.
The first stage chlorination, is uniformly passed through chlorine since initial temperature, is passed through chlorine and heating while carrying out, leads to
When the chlorine time is 1.5h, pressure reaches setting pressure in kettle, and logical chlorine dose reaches 50%-80%, the preferably 55-75% of total logical chlorine dose,
Reaction temperature is the 80%-98%, preferably 81.5-95.7% of final temperature.
The second stage chlorination, at the uniform velocity heats up, and continues to be passed through chlorine, maintains constant reaction pressure in setting pressure.
The first stage chlorination, heating rate are 1.5-2 DEG C/5min；
The second stage chlorination, heating rate are 0.5-1.2 DEG C/5min, reaction time 35-60min.
The preparation method, further include post-processing, the post-processing, resulting chliorinated polyvinyl chloride through depickling, dehydration, do
Chliorinated polyvinyl chloride finished product is obtained after dry.After gained hydrochloric acid solution is purified, into hydrochloric acid tank.
Products obtained therefrom is reacted, chlorination is uniform, and the dry powder flow of CPVC resin is less than 26s, elasticity modulus >=2500MPa,
Good, the excellent combination property of rigidity.
Solid suspension≤10mg/L after purification in hydrochloric acid solution.
Compared with prior art, beneficial effects of the present invention:
(1) dry powder flow of CPVC resin prepared by the present invention is 15-25s, elasticity modulus 2654-2816MPa, rigidity
Height, tensile strength 52-58MPa, simple beam impact strength 17-22kJ/m2；Excellent combination property.
(2) present invention is added without initiator, reduces influence of the initiator residual to combinations color and lustre and thermal stability；Simultaneously
Reaction time is short, and the chlorination reaction time is 125-150min.
(3) chlorination process concentration of hydrochloric acid is increased to 22% or more, and purification process reduces impurity, can be recycled, excess portion
Dividing can sell, and directly apply to metal metallurgy smelting, and the comprehensive utilization of hydrochloric acid is realized in organic synthesis and the production of calcium chloride etc.,
Environmental protection, energy conservation.
Specific embodiment
Embodiment 1:
(1) aaerosol solution is prepared
In chlorination tank, 4m is added3Dilute hydrochloric acid, concentration are 19%(weight ratio), polyvinyl chloride resin 700kg, polyvinyl chloride resin used gathers
Right is 1000, and mean particle size is 200 μm, and apparent density is 0.6ml/ g.Sodium polymethacrylate 4kg, talcum powder
6Kg is stirred evenly, and aaerosol solution is made.
(2) chlorination reaction
Initial reaction temperature is set as 48 DEG C, terminating reaction temperature is 85 DEG C, reaction pressure≤0.35MPa.
A, first stage chlorination
It is evacuated to -0.065MPa, reaction temperature is 48 DEG C, is passed through chlorine, is passed through chlorine and heating while carrying out.Logical chlorine 1.5h
Afterwards, leading to chlorine dose is 305kg, and reaction temperature is 76.5 DEG C, and pressure reaches 0.35MPa.
Heating rate is 1.6 DEG C/5min；
B, second stage chlorination
Adjustment heating rate is 1 DEG C/5min, continues to be passed through chlorine, holding reaction pressure is 0.35MPa；
Temperature rises to 85 DEG C, and reaction terminates, reaction time 43min.
It is 470Kg that two stages, which are passed through chlorine total amount, and the chlorinity of gained chlorinated polyvinyl chloride resin is 67.5%(weight
Than).
(3) it post-processes
Chlorinated polyvinyl chloride resin finished product, dry powder flow 19s will be obtained after chliorinated polyvinyl chloride depickling, dehydration, drying.Institute
Obtain product test performance, tensile modulus of elasticity 2750MPa；Tensile strength is 53MPa, simple beam impact strength 20kJ/m2；
After gained hydrochloric acid solution is purified, into hydrochloric acid tank.Solid suspension≤10mg/L after purification in hydrochloric acid solution.
Embodiment 2
(1) aaerosol solution is prepared
In chlorination tank, 4m is added3Dilute hydrochloric acid, concentration are 17.3%(weight ratio), polyvinyl chloride resin 960kg, polyvinyl chloride resin used
The degree of polymerization is 1300, and mean particle size is 180 μm, and apparent density is 0.63 g/ml.Polyvinylpyrrolidone 40 0g, oxygen
Change the copolymer 600g of ethylene and propylene oxide, silicone oil 3.8Kg stirs evenly, aaerosol solution is made.
(2) chlorination reaction
Initial reaction temperature is set as 50 DEG C, terminating reaction temperature is 95 DEG C, pressure≤0.4MPa.
A, first stage chlorination
It is evacuated to -0.080MPa,, reaction temperature is 50 DEG C, is passed through chlorine, is passed through chlorine and heating while carrying out.Logical chlorine
After 1.5h, leading to chlorine dose is 264kg, and reaction temperature is 81.5 DEG C, and pressure reaches 0.4MPa.
Heating rate is 1.75 DEG C/5min.
B, second stage chlorination
Adjustment heating rate is 1.2 DEG C/5min, continues to be passed through chlorine, holding reaction pressure is 0.4MPa；
Temperature rises to 95 DEG C, and reaction terminates, reaction time 56min.
It is 480Kg that two stages, which are passed through chlorine total amount, and the chlorinity of gained chlorinated polyvinyl chloride resin is 65.1%(weight
Than).
(3) it post-processes
Chlorinated polyvinyl chloride resin finished product, dry powder flow 15s will be obtained after chliorinated polyvinyl chloride depickling, dehydration, drying.Institute
Obtain product test performance, tensile modulus of elasticity 2816MPa, tensile strength 58MPa, simple beam impact strength 22kJ/m2；
After gained hydrochloric acid solution is purified, into hydrochloric acid tank.Solid suspension≤10mg/L after purification in hydrochloric acid solution.
Embodiment 3
(1) aaerosol solution is prepared
In chlorination tank, 4m is added3Dilute hydrochloric acid, concentration are 21%(weight ratio), polyvinyl chloride resin 510kg, polyvinyl chloride resin used gathers
Right is 650, and mean particle size is 220 μm, and apparent density is 0.56g/ml.The copolymer of ethylene oxide and propylene oxide
4kg, silica 7.5Kg, stirs evenly, and aaerosol solution is made.
(2) chlorination reaction
Initial reaction temperature is set as 42 DEG C, terminating reaction temperature is 81 DEG C, pressure≤0.3MPa.
A, first stage chlorination
It is evacuated to -0.070MPa, reaction temperature is 42 DEG C, is passed through chlorine, is passed through chlorine and heating while carrying out, leads to chlorine 1.5h
Afterwards, leading to chlorine dose is 300kg, and reaction temperature is 77.5 DEG C, and pressure reaches 0.3MPa.
Heating rate is 1.97 DEG C/5min.
B, second stage chlorination
Adjustment heating rate is 0.5 DEG C/5min, continues to be passed through chlorine, holding reaction pressure is 0.3MPa；
Temperature rises to 81 DEG C, and reaction terminates, reaction time 35min.
It is 400Kg that two stages, which are passed through chlorine total amount, and the chlorinity of gained chlorinated polyvinyl chloride resin is 69.1%(weight
Than).
(3) it post-processes
Chlorinated polyvinyl chloride resin finished product, dry powder flow 25s will be obtained after chliorinated polyvinyl chloride depickling, dehydration, drying.Institute
Obtain product test performance, tensile modulus of elasticity 2654MPa, tensile strength 52MPa, simple beam impact strength 17.6kJ/
m2,
After gained hydrochloric acid solution is purified, into hydrochloric acid tank.Solid suspension≤10mg/L after purification in hydrochloric acid solution.
Comparative example 1
(1) aaerosol solution is prepared
In chlorination tank, 4.1m is added3Dilute hydrochloric acid, concentration are 20%(weight ratio), polyvinyl chloride resin 850kg, Sodium methacrylate
Aaerosol solution is made in 5kg, benzoyl peroxide 1.5Kg, talcum powder 7kg, stirring, is increased to 60 DEG C, infiltration emulsification 30min；
The polyvinyl chloride resin, the degree of polymerization 700, average particle size range are 120 μm；Apparent density 0.52g/ml.
(2) chlorination reaction
Aaerosol solution is pressed into chlorination tank, after sealing, be passed through pressure be 0.1MPa nitrogen, time 30min, be evacuated to-
0.06MPa excludes the oxygen in chlorination tank.
In chlorination process, the initial temperature T0 of reaction is 60 DEG C, and temperature T1 is 90 DEG C, and temperature T2 is 100 DEG C, end reaction
Temperature T3 is 110 DEG C.Setting always logical chlorine dose, as 570kg, the logical chlorine dose in the section T0-T1 is 208kg, and leading to the chlorine time is 1.3h,
Logical chlorine dose in the section T1-T2 is 253kg, and leading to the chlorine time is 1.1h, and the logical chlorine dose in the section T2-T3 is 109kg, leads to the chlorine time
For 1.3h.Logical chlorine terminates, and keeps the temperature 10min.Pressure≤0.4MPa in reaction process kettle.
(3) it post-processes
Chlorinated polyvinyl chloride resin finished product, gained chliorinated polyvinyl chloride tree will be obtained after chliorinated polyvinyl chloride depickling, dehydration, drying
The chlorinity of rouge is 67.8%(weight ratio), dry powder flow 40s, products obtained therefrom test performance tensile modulus of elasticity is
2289MPa, tensile strength 55MPa, simple beam impact strength 13kJ/m2。
Comparative example 1 joined initiator, while need through impregnation process, and initial temperature and outlet temperature are above this hair
It is bright, chlorine, heating control and pressure control are led in chlorination reaction and is different from the present invention, the chlorinated polyvinyl chloride resin of preparation is done
Powder mobility is bad, and tensile modulus of elasticity is low, and rigidity declines, and simple beam impact strength also reduces, meanwhile, the chlorination reaction time is
3.86h。
Claims (10)
1. a kind of preparation method of chliorinated polyvinyl chloride, it is characterised in that: the preparation method, comprising the following steps: preparation is outstanding
Floating solution, chlorination reaction；The chlorination reaction, including first stage chlorination, second stage chlorination.
2. a kind of preparation method of chliorinated polyvinyl chloride according to claim 1, it is characterised in that: raw material polyvinyl chloride resin
The degree of polymerization is 500-2500；Average particle size range is 160 μm -230 μm, apparent density 0.55g/ml-0.65g/ml.
3. a kind of preparation method of chliorinated polyvinyl chloride according to claim 1, it is characterised in that: the chlorination reaction,
The initial temperature of reaction is 40 DEG C -50 DEG C, and reaction terminating temperature is 80 DEG C -100 DEG C, sets 0.3~0.4MPa of pressure, leads to chlorine dose
Weight ratio with polyvinyl chloride resin is 0.4-0.9.
4. a kind of preparation method of chliorinated polyvinyl chloride according to claim 1, it is characterised in that: the first stage chlorine
Change, chlorine is uniformly passed through since initial temperature, be passed through chlorine and heating while carrying out, when the logical chlorine time is 1.5h, kettle internal pressure
Power reaches setting pressure, and logical chlorine dose reaches the 50%-80% of total logical chlorine dose, and reaction temperature is the 80%-98% of final temperature.
5. a kind of preparation method of chliorinated polyvinyl chloride according to claim 1, it is characterised in that: the second stage chlorine
Change, at the uniform velocity heat up, continue to be passed through chlorine, maintains constant reaction pressure in setting pressure.
6. a kind of preparation method of chliorinated polyvinyl chloride according to claim 4, it is characterised in that: the first stage chlorine
Change, heating rate is 1.5-2 DEG C/5min.
7. a kind of preparation method of chliorinated polyvinyl chloride according to claim 5, it is characterised in that: the second stage chlorine
Change, heating rate is 0.5-1.2 DEG C/5min, reaction time 35-60min.
8. a kind of preparation method of chliorinated polyvinyl chloride according to claim 1, it is characterised in that: the preparation suspends molten
Hydrochloric acid solution is added in liquid, and polyvinyl chloride resin, dispersing agent, antitack agent stir evenly, aaerosol solution are made；The matter of the hydrochloric acid solution
Amount concentration is 16%-21%.
9. a kind of preparation method of chliorinated polyvinyl chloride according to claim 8, it is characterised in that:
The dosage of the dispersing agent is the 0.02%-1.0% of polyvinyl chloride resin, and the dosage of the anti-adhesion agent is the 0.08%- of polyvinyl chloride resin
1.6%, the weight ratio of the polyvinyl chloride resin and hydrochloric acid solution is 1:3-1:9.
10. a kind of preparation method of chliorinated polyvinyl chloride according to claim 8, it is characterised in that:
The dispersing agent is the copolymer of neopelex, sodium polymethacrylate, ethylene oxide and propylene oxide, gathers
One or two kinds of combinations of vinylpyrrolidone, polyether surfactant；
The anti-adhesion agent is one of talcum powder, silica, silicone oil.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116675941A (en) * | 2023-08-03 | 2023-09-01 | 山东亚大新材料有限公司 | Method for preparing chlorinated polyvinyl chloride by acid phase suspension method |
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| CN104011091A (en) * | 2011-12-02 | 2014-08-27 | 德山积水工业株式会社 | Method for producing chlorinated vinyl chloride-based resin |
| CN106103501A (en) * | 2014-03-31 | 2016-11-09 | 积水化学工业株式会社 | The manufacture method of chlorinated vinyl chloride resins |
| CN106632746A (en) * | 2017-01-04 | 2017-05-10 | 阳泉煤业（集团）有限责任公司 | Preparation method of chlorinated polyvinyl chloride |
| CN109369829A (en) * | 2018-10-26 | 2019-02-22 | 山东高信化学股份有限公司 | The injection molding preparation method of high-performance chlorinated polyvinyl chloride |
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Patent Citations (4)
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| CN104011091A (en) * | 2011-12-02 | 2014-08-27 | 德山积水工业株式会社 | Method for producing chlorinated vinyl chloride-based resin |
| CN106103501A (en) * | 2014-03-31 | 2016-11-09 | 积水化学工业株式会社 | The manufacture method of chlorinated vinyl chloride resins |
| CN106632746A (en) * | 2017-01-04 | 2017-05-10 | 阳泉煤业（集团）有限责任公司 | Preparation method of chlorinated polyvinyl chloride |
| CN109369829A (en) * | 2018-10-26 | 2019-02-22 | 山东高信化学股份有限公司 | The injection molding preparation method of high-performance chlorinated polyvinyl chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116675941A (en) * | 2023-08-03 | 2023-09-01 | 山东亚大新材料有限公司 | Method for preparing chlorinated polyvinyl chloride by acid phase suspension method |
| CN116675941B (en) * | 2023-08-03 | 2023-10-31 | 山东亚大新材料有限公司 | Method for preparing chlorinated polyvinyl chloride by acid phase suspension method |
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