CN108530569A - A kind of 110m3The method that polymeric kettle produces SG-5 type polyvinyl chloride - Google Patents
A kind of 110m3The method that polymeric kettle produces SG-5 type polyvinyl chloride Download PDFInfo
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- CN108530569A CN108530569A CN201810213895.5A CN201810213895A CN108530569A CN 108530569 A CN108530569 A CN 108530569A CN 201810213895 A CN201810213895 A CN 201810213895A CN 108530569 A CN108530569 A CN 108530569A
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- polymeric kettle
- polyvinyl chloride
- deionized water
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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
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
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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
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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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses a kind of 110m3The method that polymeric kettle produces 5 type polyvinyl chloride of SG, belongs to the 5 type PVC Process Technology fields SG.It includes the following steps：(1) initiator is prepared；(2) pan feeding operates；(3) warming temperature.The method of the present invention, both reduces 110m3Polymeric kettle produces the production cost of 5 type polyvinyl chloride of SG, also reduces the molecular weight distribution width of Corvic product, improves the quality of Corvic product.
Description
Technical field
The present invention relates to a kind of 110m3The method that polymeric kettle produces SG-5 type polyvinyl chloride, belongs to SG-5 type polyvinyl chloride
Production technical field.
Background technology
Polyvinyl chloride, English abbreviation PVC (Polyvinyl chloride) are vinyl chloride monomer (vinyl chloride
Monomer, abbreviation VCM) in initiators such as peroxide, azo-compounds；Or Raolical polymerizable is pressed under light, heat effect
The polymer that mechanism is polymerized.Ryuron and vinyl chloride copolymer system are referred to as vinyl chloride resin.
Polyvinyl chloride is one of maximum plastic product of yield in the world, cheap, is widely used.Polyvinyl chloride is white
Color or buff powder cannot individually use, it is necessary to by being modified.Polyvinyl chloride is the white powder of impalpable structure, branched
Degree is smaller, poor to the stability of light and heat.Different additives can be added according to different purposes, different physics can be presented
Performance and mechanical property.Suitable plasticizer is added in Corvic, can be made into a variety of hard, soft and transparent system
Product.Each model of Corvic point, in China, wherein the most common one is SG-5, and application range is relatively broad, because of demand
It is different and use different models.Such as SG5 (K-65, S1000) is applied to tubing, proximate matter, plank etc., and SG3 (K-70,
S1300 it is mostly) soft product, is applied to manufacture hose, electric wire, film, footwear material, toy, auto parts machinery more.
Currently, country 110m3The flow of polymeric kettle production SG-5 type resins is commonly cold deionized water (dispersant, initiation
Agent is added in cold deionized water pipeline and is added in polymeric kettle together with cold deionized water) → vinyl chloride monomer → hot deionized water,
Pan feeding process used time 55min.Its initiator generally uses TX-23 and TX-99 compound systems.Wherein, TX-23, i.e. peroxidating are new
Certain herbaceous plants with big flowers tert-butyl acrylate (English name tert-Butyl peroxyneodecanoate), molecular formula C14H28O3；TX-99, i.e. peroxidating
Pungent certain herbaceous plants with big flowers acid isopropyl phenyl ester (English name Cumyl peroxyneodecanoate), molecular formula C19H28O4。
The above method there are the problem of：First, the initiator addition of the technique is by cold plain water lines, in cold no ion
Water is just added in kettle when being added, and then adds monomer, finally starts hot deionized water and pumps 120 DEG C of overheats of addition into polymeric kettle
Deionized water, after the completion of hot deionized water is added polymerization temperature in the kettle close to reaction temperature (setting reaction temperature T ± 2 DEG C),
Into the stage of reaction, entire pan feeding process time is longer in 55min or so.After the completion of cold deionized water pan feeding, vinyl chloride list
Body is added in polymeric kettle, and polymeric kettle temperature not up to sets reaction temperature at this time, and due to the presence of initiator, vinyl chloride monomer exists
Less than polymerisation is proceeded by under conditions of setting reaction temperature, until could be anti-in setting after the completion of hot deionized water pan feeding
It answers and carries out polymerisation in temperature range, the Corvic of the higher viscosity number of part vinyl chloride monomer reaction generation during this,
Corvic product molecular weight distribution width is caused to increase, the processing performance of Corvic and the stability of product become
Difference.Second is that initiator uses TX-23 and TX-99 compound systems, in order to ensure the service efficiency of polymeric kettle, control polymeric kettle reaction
Time, general total addition was in 46kg, and cost is generally higher, about 57.4 yuan/ton of polyvinyl chloride within 260min.
In consideration of it, it is necessary to research and develop a kind of new 110m3The method that polymeric kettle produces SG-5 type polyvinyl chloride, it is existing to solve
There is the deficiency of technology.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of 110m3Polymeric kettle produces SG-5 type polychlorostyrene second
The method of alkene.The method of the present invention, both reduces 110m3Polymeric kettle produces the production cost of SG-5 type polyvinyl chloride, also reduces
The molecular weight distribution width of Corvic product, improves the quality of Corvic product.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of 110m3Polymeric kettle produces SG-5 type polychlorostyrene second
The method of alkene, includes the following steps：
(1) initiator is prepared：In mass ratio 1:(1-3.5) weighs EHP and TX-99, after mixing, obtains EHP respectively
With TX-99 compound systems；
(2) pan feeding operates：By cold deionized water, 2-4kg buffers, 7-9kg dispersant As, 28-32kg dispersant Bs and 3-
110m is added simultaneously in 4kg dispersing agent Cs3In polymeric kettle, when the addition of cold deionized water is 10-15m3When, then by 46kg steps
(1) EHP the and TX-99 compound systems obtained are added in polymeric kettle, then proceed to add cold deionized water to 20m3, it is eventually adding
40-44 tons of monomers are uniformly mixed, wherein the temperature of the cold deionized water is 30-45 DEG C；
(3) warming temperature：18-20m is added into polymeric kettle3Hot deionized water, in 55-59 DEG C of polymerisation 240-
To get to the SG-5 types polyvinyl chloride after 280min.
In the step (1) of the present invention, TX-23 and TX-99 in the prior art is replaced using EHP and TX-99 compound systems
Compound system.Wherein, EHP, i.e. dicetyl peroxydicarbonate two (2- ethylhexyls) ester (entitled bis (2-ethylhexyl) of English
Peroxydicarbonate), molecular formula C18H34O6, half-life period and activity performance and TX-23 are essentially identical.EHP autoaccelerations
Decomposition temperature is 5 DEG C, can be decomposed rapidly at room temperature, decomposition product CO2With 2-Ethylhexyl Alcohol (having special odor).Using
Corvic product quality aspect is had no significant effect after the system, and the price of EHP is the half of TX-23 prices,
The cost of polyvinyl chloride is greatly reduced under the premise of ensuring product quality using EHP and TX-99 compound systems.EHP and TX-
23 performance comparison refers to table 1.
The property of table 1 EHP and TX-23 compares
In the step (2) of the present invention, when cold deionized water addition is 10-15m3When, it is initially added into initiator.Postponement is drawn
Send out agent the addition time, can shorten initiator with part vinyl chloride monomer at low temperature react generation higher degrees of polymerization when
Between, the molecular weight distribution width of Corvic product is reduced, the quality of Corvic product is improved.
In the step (2) of the present invention, the temperature for controlling cold deionized water is 30-45 DEG C, is because initiator is lower
At a temperature of be easy for decomposing, water temperature control it is too low, during pan feeding kettle temperature also not up to setting reaction temperature when, monomer is in kettle
The Corvic for forming higher degrees of polymerization, " flake " is caused in Downstream processing, influences Downstream processing.Present invention
People obtains cold deionized water temperature control at 30-45 DEG C by constantly experiment, and product flake index is within the scope of top grade.
Based on the above technical solution, the present invention can also be improved as follows.
Further, in step (2) EHP the and TX-99 compound systems EHP and TX-99 mass ratio 1:2.
It is using above-mentioned further advantageous effect：Above-mentioned is optimal parameter.The EHP and TX- obtained using above-mentioned parameter
The performance of 99 compound systems is best.
Further, the weight of step (2) described buffer is 3kg；The weight of the dispersant A is 8kg；The dispersant
The weight of B is 30kg；The weight of the dispersing agent C is 3.5kg；The addition of the cold deionized water is 12m3When, then will
EHP the and TX-99 compound systems that 46kg steps (1) obtain are added in polymeric kettle；The weight of the monomer is 42 tons.
Further, the buffer is one kind in ammonium hydrogen carbonate, sodium bicarbonate, sodium hydroxide, and the dispersant A is
The polyvinyl alcohol of alcoholysis degree 69-74%, the dispersant B are the polyvinyl alcohol of alcoholysis degree 78.5-81.5%, the dispersing agent C
For the polyvinyl alcohol of alcoholysis degree 38-40%, the monomer is vinyl chloride.
It is using above-mentioned further advantageous effect：The polyvinyl alcohol of above-mentioned alcoholysis degree is selected, can not only be shown poly-
The superiority of vinyl alcohol, moreover it is possible to reach most economical cost-effectiveness while ensureing high-quality product quality.
Further, the dispersant A is one kind in BR-70, PVAL7206, TCR-7507P, L-10.Wherein, BR-
70 and TCR-7507P is purchased from Yunnan Zheng Bang Science and Technology Ltd.s.PVAL7206 and L-10 is purchased from Kuraray company.
Further, the dispersant B is one kind in BR-80, PVAL4788, TCR-7524P, GH-20.Wherein, BR-
80 and TCR-7524P is purchased from Yunnan Zheng Bang Science and Technology Ltd.s.PVAL4788 and GH-20 is purchased from Kuraray company.
Further, the dispersing agent C is one kind in BR-40, PVAL55, TCR-4040, LW-200.Wherein, BR-40
It is purchased from Yunnan Zheng Bang Science and Technology Ltd.s with TCR-4040.PVAL55 and LW-200 is purchased from Kuraray company.
Further, the temperature of step (3) the hot deionized water is 100-130 DEG C, weight 19m3, the polymerisation
Temperature be 57 DEG C, time of reaction is 260min.
Beneficial effects of the present invention：
(1) present invention is for the first time in 110m3Polymeric kettle produces in the method for SG-5 type polyvinyl chloride, multiple using EHP and TX-99
Zoarium system is used as initiator, and the production cost of SG-5 types polyvinyl chloride per ton is reduced 20 yuan.
(2) present invention optimizes 110m3Polymeric kettle produces the pan feeding program in the method for SG-5 type polyvinyl chloride, will cause
The agent pan feeding time postpones to the addition of cold water later stage is played, and reacts generation at low temperature with part vinyl chloride monomer so as to shorten initiator
The time of higher degrees of polymerization reduces the molecular weight distribution width of Corvic product, improves Corvic production
The quality of product.
Specific implementation mode
Principles and features of the present invention are described below in conjunction with specific embodiment, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1
The 110m of the present embodiment3The method that polymeric kettle produces SG-5 type polyvinyl chloride, includes the following steps：
(1) initiator is prepared：In mass ratio 1:1, EHP and TX-99 are weighed respectively, after mixing, obtain EHP and TX-
99 compound systems；
(2) pan feeding operates：By 30 DEG C of cold deionized waters, 2kg ammonium hydrogen carbonate, 9kg BR-70 (purchased from the positive nation's science and technology in Yunnan
Co., Ltd), 28kg BR-80 (be purchased from Yunnan Zheng Bang Science and Technology Ltd.s) and 4kg BR-40 (have purchased from the positive nation's science and technology in Yunnan
Limit company) while 110m is added3In polymeric kettle, when the addition of cold deionized water is 10m3When, then 46kg steps (1) are obtained
EHP and TX-99 compound systems be added in polymeric kettle, then proceed to plus cold deionized water be to 20m3, it is eventually adding 40 tons of chloroethenes
Alkene is uniformly mixed, wherein 30 DEG C of the temperature ＞ of the cold deionized water；
(3) warming temperature：18m is added into polymeric kettle3The hot deionized water that temperature is 100 DEG C, in 55 DEG C of polymerisations
To get to the SG-5 types polyvinyl chloride after 280min.
Embodiment 2
The 110m of the present embodiment3The method that polymeric kettle produces SG-5 type polyvinyl chloride, includes the following steps：
(1) initiator is prepared：In mass ratio 1:2, EHP and TX-99 are weighed respectively, after mixing, obtain EHP and TX-
99 compound systems；
(2) pan feeding operates：38 DEG C of cold deionized waters, 2kg sodium bicarbonates, 8kg PVAL7206 are (laughable purchased from Japan
Beautiful company), 30kg PVAL4788 (be purchased from Kuraray company) and 3.5kg PVAL55 (being purchased from Kuraray company) together
When 110m is added3In polymeric kettle, when the addition of cold deionized water is 12m3When, then EHP and TX- that 46kg steps (1) are obtained
99 compound systems are added in polymeric kettle, then proceed to add cold deionized water to 20m3, 42 tons of vinyl chloride are eventually adding, mixing is equal
It is even, wherein 30 DEG C of the temperature ＞ of the cold deionized water；
(3) warming temperature：19m is added into polymeric kettle3The hot deionized water that temperature is 115 DEG C, in 57 DEG C of polymerisations
To get to the SG-5 types polyvinyl chloride after 260min.
Embodiment 3
The 110m of the present embodiment3The method that polymeric kettle produces SG-5 type polyvinyl chloride, includes the following steps：
(1) initiator is prepared：In mass ratio 1:3.5, weigh EHP and TX-99 respectively, after mixing, obtain EHP and
TX-99 compound systems；
(2) pan feeding operates：45 DEG C of cold deionized waters, 4kg sodium hydroxides, 7kgTCR-7507P (are purchased from the positive nation in Yunnan
Science and Technology Ltd.), 32kg GH-20 (be purchased from Kuraray company) and 3kg TCR-4040 (have purchased from the positive nation's science and technology in Yunnan
Limit company) while 110m is added3In polymeric kettle, when the addition of cold deionized water is 15m3When, then 46kg steps (1) are obtained
EHP and TX-99 compound systems be added in polymeric kettle, then proceed to plus cold deionized water be to 20m3, it is eventually adding 44 tons of chloroethenes
Alkene is uniformly mixed, wherein 30 DEG C of the temperature ＞ of the cold deionized water；
(3) warming temperature：20m is added into polymeric kettle3The hot deionized water that temperature is 130 DEG C, in 59 DEG C of polymerisations
To get to the SG-5 types polyvinyl chloride after 240min.
Comparative example 1
As different from Example 2, the initiator of the step of comparative example 1 (1) uses TX-23 and TX-99 compound systems,
Its step is all identical.The calculation formula of initiator amount is：
In formula, I is initiator amount, %；
Nr is initiator theoretical consumption, (1 ± 0.1) mol/ tons of polyvinyl chloride；When using EHP, 1.1mol/ tons of polychlorostyrene are taken
Ethylene；
M is the relative molecular mass of initiator；
T is polymerization time, h；
t0.5For decomposition of initiator half-life period, h.
The polyvinyl chloride per ton of embodiment 2 and comparative example 1 consumes the Cost comparisons of initiator, as shown in table 2.
The Cost comparisons of table 2 embodiment 2 and comparative example 1
| Embodiment 1 | Comparative example 1 | |
| Initiator price (yuan/ton) | 18803 | 41026 |
| Per kettle price aggregate (member) | 611 | 1333 |
| Consume the cost price (yuan/ton polyvinyl chloride) of initiator | 17 | 37 |
It can be seen that the present invention is in 110m3Polymeric kettle produces in the method for SG-5 type polyvinyl chloride, using EHP and TX-99
Compound system reduces 20 yuan as initiator, by the production cost of SG-5 types polyvinyl chloride per ton.
Comparative example 2
As different from Example 2, in the step of comparative example 2 (2), when reaction kettle is added in cold deionized water, that is, start
Initiator is added, other steps are all identical.Obtained product molecular weight distribution, as shown in table 3.
The molecular weight distribution for the product that 3 embodiment 2 of table is obtained with comparative example 2 compares
| 60 mesh | 80 mesh | 100 mesh | 120 mesh | 140 mesh | 160 mesh | 180 mesh | 200 mesh | 250 mesh | |
| Embodiment 2 | 0.14 | 0.49 | 0.74 | 33.89 | 54.92 | 4.81 | 2.47 | 1.63 | 0.9 |
| Comparative example 2 | 0.11 | 0.29 | 1.87 | 22.85 | 52.48 | 13.31 | 3.81 | 2.5 | 2.69 |
It can be seen that the present invention by the initiator pan feeding time postpone to beat the cold water later stage be added, so as to shorten initiator with
Part vinyl chloride monomer reacts the time for generating higher degrees of polymerization at low temperature, reduces the molecular weight of Corvic product
The dispersion of distribution improves the quality of Corvic product.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of 110m3The method that polymeric kettle produces SG-5 type polyvinyl chloride, which is characterized in that include the following steps：
(1) initiator is prepared：In mass ratio 1:(1-3.5) weighs EHP and TX-99 respectively, after mixing, obtain EHP and
TX-99 compound systems；
(2) pan feeding operates：By cold deionized water, 2-4kg buffers, 7-9kg dispersant As, 28-32kg dispersant Bs and 3-4kg points
110m is added simultaneously in powder C3In polymeric kettle, when the addition of cold deionized water is 10-15m3When, then 46kg steps (1) are obtained
EHP and TX-99 compound systems be added in polymeric kettle, then proceed to plus cold deionized water be to 20m3, it is eventually adding 40-44 tons of lists
Body is uniformly mixed, wherein the temperature of the cold deionized water is 30-45 DEG C；
(3) warming temperature：18-20m is added into polymeric kettle3Hot deionized water, after 55-59 DEG C of polymerisation 240-280min,
Obtain the SG-5 types polyvinyl chloride.
2. a kind of 110m according to claim 13The method that polymeric kettle produces SG-5 type polyvinyl chloride, which is characterized in that step
Suddenly in (2) described EHP and TX-99 compound systems EHP and TX-99 mass ratio 1:2.
3. a kind of 110m according to claim 13The method that polymeric kettle produces SG-5 type polyvinyl chloride, which is characterized in that step
Suddenly the weight of (2) described buffer is 3kg；The weight of the dispersant A is 8kg；The weight of the dispersant B is 30kg；Institute
The weight for stating dispersing agent C is 3.5kg；The addition of the cold deionized water is 12m3When, then 46kg steps (1) are obtained
EHP and TX-99 compound systems are added in polymeric kettle；The weight of the monomer is 42 tons.
4. a kind of 110m according to claim 1 or 33The method that polymeric kettle produces SG-5 type polyvinyl chloride, feature exist
In the buffer is one kind in ammonium hydrogen carbonate, sodium bicarbonate, sodium hydroxide, and the dispersant A is alcoholysis degree 69-74%
Polyvinyl alcohol, the dispersant B be alcoholysis degree 78.5-81.5% polyvinyl alcohol, the dispersing agent C be alcoholysis degree 38-
40% polyvinyl alcohol, the monomer are vinyl chloride.
5. a kind of 110m according to claim 13The method that polymeric kettle produces SG-5 type polyvinyl chloride, which is characterized in that step
Suddenly the temperature of (3) described hot deionized water is 100-130 DEG C, weight 19m3, the temperature of the polymerisation is 57 DEG C, reaction
Time be 260min.
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| CN201711466539 | 2017-12-28 | ||
| CN2017114665396 | 2017-12-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793157A (en) * | 2020-07-03 | 2020-10-20 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of SG5 type polyvinyl chloride resin with high plasticizing performance |
| CN113354760A (en) * | 2021-06-28 | 2021-09-07 | 天伟化工有限公司 | Method for regulating and controlling micro-nano structure of polyvinyl chloride resin particles |
| CN113388056A (en) * | 2021-06-28 | 2021-09-14 | 天伟化工有限公司 | Production method of special resin for gas-solid phase chlorinated polyvinyl chloride with medium and high polymerization degrees |
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| CN103408681A (en) * | 2013-07-23 | 2013-11-27 | 沈阳化工大学 | Method for largely raising polyvinyl chloride productivity |
| CN104028173A (en) * | 2014-05-28 | 2014-09-10 | 新疆中泰化学股份有限公司 | Polymerizer feeding device and using method thereof |
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| CN102492066A (en) * | 2011-12-08 | 2012-06-13 | 内蒙古宜化化工有限公司 | Method for preparing polyvinyl chloride by suspension polymerization |
| CN103408681A (en) * | 2013-07-23 | 2013-11-27 | 沈阳化工大学 | Method for largely raising polyvinyl chloride productivity |
| CN104028173A (en) * | 2014-05-28 | 2014-09-10 | 新疆中泰化学股份有限公司 | Polymerizer feeding device and using method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111793157A (en) * | 2020-07-03 | 2020-10-20 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of SG5 type polyvinyl chloride resin with high plasticizing performance |
| CN111793157B (en) * | 2020-07-03 | 2022-03-01 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of SG5 type polyvinyl chloride resin with high plasticizing performance |
| CN113354760A (en) * | 2021-06-28 | 2021-09-07 | 天伟化工有限公司 | Method for regulating and controlling micro-nano structure of polyvinyl chloride resin particles |
| CN113388056A (en) * | 2021-06-28 | 2021-09-14 | 天伟化工有限公司 | Production method of special resin for gas-solid phase chlorinated polyvinyl chloride with medium and high polymerization degrees |
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Application publication date: 20180914 |