CN106279490A - A kind of preparation method of suspension method vinyl chloride acrylic N-butyl copolymer resins - Google Patents
A kind of preparation method of suspension method vinyl chloride acrylic N-butyl copolymer resins Download PDFInfo
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- CN106279490A CN106279490A CN201610688034.3A CN201610688034A CN106279490A CN 106279490 A CN106279490 A CN 106279490A CN 201610688034 A CN201610688034 A CN 201610688034A CN 106279490 A CN106279490 A CN 106279490A
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- copolymer resins
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- butyl
- acrylic acid
- 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
- C08F214/00—Copolymers 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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- 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
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
Abstract
The present invention provides the preparation method of a kind of suspension method vinyl chloride acrylic N-butyl copolymer resins, belongs to chemical industry macromolecule synthesising technology field.The present invention uses process for suspension polymerization, technology is added by adjusting and optimizing polymerization formula and control n-butyl acrylate, the vinyl chloride acrylic N-butyl copolymer resins product of preparation, form is regular, centralized particle diameter, transparent shape, and there is higher apparent density and lower oil absorbency, show obvious internal plasticization and erosion-resisting characteristics.
Description
Technical field:
The present invention relates to the preparation of a kind of suspension method and there is the preparation of internally plasticized vinylchloride-acrylic acid N-butyl copolymer resins
Method, belongs to chemical industry macromolecule synthesising technology field.
Background technology
Polrvinyl chloride (PVC) has the comprehensive mechanical property of excellence, and anti-flammability, chemical resistance and cheap because of it
Etc. the every field being widely used in people's lives.But the drawbacks such as resins for universal use fragility is big, impact resilience is poor, intensity is low are seriously made
The about Corvic development at specific areas such as impact modified, flexible soft goods.
Generally use blending toughening Corvic, or use low molecular compound plasticising to can overcome the disadvantages that universal tree with preparation
The defect that fat fragility is big, has compliance, increasing tougheness concurrently, has rubber like elastomeric flexible Corvic.But processing and
In application process, little molecule class plasticizer easily oozes out, migrates to product surface, causes the decline of product properties；Meanwhile, such as DOP
Little molecule plasticizers such as (dioctyl phthalates) has certain toxicity, can cause certain injury and pollution.
Vinyl chloride and acrylic ester monomer copolymerization, can introduce long-chain aliphatic acrylate in PVC strand, can
Give copolymer resins preferable internal plasticization performance, vinyl chloride copolymer can also be made simultaneously to have excellent shock resistance, resistance to concurrently
The features such as ageing properties, tolerance to cold, lasting compliance, good processability.
The most international, domestic all have Patents report vinyl chloride and the synthetic method of acrylate, domestic Zhejiang University
With the numerous studies that there is laboratory stage in part company, all to copolymerization process, copolymerization formula, resin particle form, resin property
Etc. having carried out comprehensive study.But the 70m that domestic PVC industry is general at present3The industry of lot-size on polyplant
Produce popularization and application report to be still rarely reported.
Chinese patent CN104250334A vinyl chloride-acrylate analog copolymer and preparation method thereof, it was recently reported that chlorine
Ethylene and acrylic ester monomer copolymerization, the addition to acrylic ester monomer has been done more in-depth study, but has the most simply been stopped
Stay laboratory stage, it is impossible to accomplish seriality industrialized production and obtain more uniform copolymer resin.
In patent CN103814051A copolymer resin based on vinyl chloride and preparation method thereof, it is provided that one has
The preparation method of the vinyl chloride-acrylate copolymer of nucleocapsid structure, but loaded down with trivial details being difficult to of its two-stage polymerization method operates；Simultaneously its
Owing to needs prepare " suspension stabilizer " in advance, it is impossible to fast and stable is prior according to polymerization during actual industrial metaplasia is produced
Response situation and adjust corresponding formula.
Although the industrialized production of document vinyl chloride-propylene acid butyl ester copolymer resins reports employing 7m3Device tries
Produce vinyl chloride-propylene acid butyl ester copolymer resins, but do not specifically give its formula and associated control parameters, its polyreaction simultaneously
During adjust and control temperature and can cause the inequality of molecular weight distribution and cause the defect of strand, thus affect copolymerization
Resin quality.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of suspension method vinylchloride-acrylic acid N-butyl copolymer resins
Preparation method.
Technical scheme is as follows:
The preparation method of a kind of suspension method vinylchloride-acrylic acid N-butyl copolymer resins, comprises the following steps:
(1) after pure water, Vinyl Chloride Monomer, dispersant, initiator A metering, it is separately added into polymeric kettle, controls reaction temperature
Being 45～70 DEG C, polymerization process starts water filling after starting, and polyreaction starts to 180min to add propylene the most continuously
Acid N-butyl, when polyreaction is carried out to 90min～120min, adds a certain amount of initiator B；
(2) after polyreaction 300min, adding terminator after pressure drop 0.05～0.15MPa, after stirring, discharging is extremely
Slurry tank, through stripping by the Vinyl Chloride Monomer desorption in copolymer resins, sends into drying system and is dried.
Wherein, pure water in step (1): 110～150 mass parts, Vinyl Chloride Monomer: 100 mass parts, dispersant: 0.07～
0.1 mass parts, initiator A (50% aqueous solution): 0.08～0.11 mass parts, water filling: 25～50 mass parts, initiator B (50%
Aqueous solution): 0.003～0.006 mass parts, n-butyl acrylate: 3～5 mass parts；
Described dispersant selected from hydroxypropyl methyl cellulose (methoxyl content is 27～30%, hydroxypropyl content be 4～
7.5%), alcoholysis degree be 79～81 polyvinyl alcohol, alcoholysis degree be 71.5～73.5 polyvinyl alcohol, alcoholysis degree be 45～51
In polyvinyl alcohol three kinds or four kinds are combined.
Described initiator A is: peroxy dicarbonate two (2-ethyl hexyl) ester (EHP), cumyl peroxyneodecanoate
(CNP) two kinds of mixing；
Described initiator B is: cumyl peroxyneodecanoate (CNP)；
Described terminator is: α-methyl styrene content is the aqueous solution of 12%.
Beneficial effect
The present invention utilizes the 70m that PVC Industry is general3Polyplant, by adjusting polymerization formula, using suspends gathers
Close technique, omnidistance DCS automatically controls, enclosed charging and etc. warm water fed technology, it is achieved the n-butyl acrylate that reactivity ratio is higher
The automatically controlling of different additions, and in polymerization process, the stream of initiator solution adds.Preparation method of the present invention can
Strong operability, plant automation degree is high easy and simple to handle the most easy to control, and polyreaction is stable, and product batches yield is big, batch
Between difference little, it is easy to industrial-scale production, the vinylchloride-acrylic acid N-butyl copolymer resins constant product quality of preparation,
Copolymerization effect is obvious, and the most transparent shape of copolymer resins granule, form is regular, centralized particle diameter, and has higher apparent
Density and lower oil absorbency, show obvious internal plasticization and erosion-resisting characteristics.
Detailed description of the invention
Below by instantiation, the present invention is further described, wherein with embodiment 3 as most preferred embodiment.
Embodiment 1
After polymeric kettle is totally available, using omnidistance enclosed charging and wait warm water fed technology, DCS programme-control is the most automatic
Adding isothermal pure water 130 parts, Vinyl Chloride Monomer 100 parts, dispersant 0.07 part, wherein, hydroxypropyl methyl cellulose, alcoholysis degree are
The polyvinyl alcohol mass ratio that polyvinyl alcohol that the polyvinyl alcohol of 79～81, alcoholysis degree are 71.5～73.5, alcoholysis degree are 45～51
For 1:6.6:3.8:1.3, initiator A 0.09 part (EHP Yu CNP mass ratio is 2.5:1), i.e. reach 57 DEG C when polymerization charge is complete
Polymerization temperature；Starting water filling after polyreaction starts, polyreaction starts to 180min to add acrylic acid the most continuously
N-butyl 3.0 parts；When polyreaction 90min, stream adds 0.003 part of initiator B (cumyl peroxyneodecanoate CNP)；Stirring
Mixing and cool down under water effect, polymerization temperature controls at 57 DEG C, and after polymerization reaction time 300min, polymerization water filling reaches 35 parts, poly-
Adding terminator after closing reaction pressure fall 0.1MPa and terminate reaction, discharging to slurry tank, after stripping, dry packing i.e. obtains copolymerization
Naval stores.
Embodiment 2
After polymeric kettle is totally available, using omnidistance enclosed charging and wait warm water fed technology, DCS programme-control is the most automatic
Adding isothermal pure water 130 parts, Vinyl Chloride Monomer 100 parts, dispersant 0.07 part, wherein hydroxypropyl methyl cellulose, alcoholysis degree are
The polyvinyl alcohol mass ratio that polyvinyl alcohol that the polyvinyl alcohol of 79～81, alcoholysis degree are 71.5～73.5, alcoholysis degree are 45～51
For 1:6.6:3.8:1.3, initiator A 0.09 part (EHP Yu CNP mass ratio is 2.5:1), i.e. reach 57 DEG C when polymerization charge is complete
Polymerization temperature；Starting water filling after polyreaction starts, polyreaction starts to 180min to add acrylic acid the most continuously
N-butyl 5.0 parts；When polyreaction 90min, stream adds 0.005 part of initiator B (CNP)；Under stirring and cooling water effect, poly-
Closing temperature and control at 57 DEG C, after polymerization reaction time 300min, polymerization water filling reaches 35 parts, after polymerization pressure fall 0.1MPa
Adding terminator and terminate reaction, discharging to slurry tank, after stripping, dry packing i.e. obtains copolymer resins product.
Embodiment 3
After polymeric kettle is totally available, using omnidistance enclosed charging and wait warm water fed technology, DCS programme-control is the most automatic
Adding isothermal pure water 130 parts, Vinyl Chloride Monomer 100 parts, dispersant 0.09 part, wherein hydroxypropyl methyl cellulose, alcoholysis degree are
The polyvinyl alcohol mass ratio that polyvinyl alcohol that the polyvinyl alcohol of 79～81, alcoholysis degree are 71.5～73.5, alcoholysis degree are 45～51
For 1:6.6:3.2:1.1, initiator A 0.1 part (EHP Yu CNP mass ratio is 2.5:1), i.e. reach 57 DEG C when polymerization charge is complete
Polymerization temperature；Starting water filling after polyreaction starts, polyreaction starts to 180min to add acrylic acid the most continuously
N-butyl 5.0 parts；When polyreaction 90min, stream adds 0.005 part of initiator B (CNP)；Under stirring and cooling water effect, poly-
Closing temperature and control at 57 DEG C, after polymerization reaction time 300min, polymerization water filling reaches 35 parts, after polymerization pressure fall 0.1MPa
Adding terminator and terminate reaction, discharging to slurry tank, after stripping, dry packing i.e. obtains copolymer resins product.
By the copolymer resins product obtained by the inventive method, through GB/T 5761-2006 " the universal polychlorostyrene of suspension method
Vinyl " it is detected, its test result and general SG5 type resin index contrast and are:
| General SG5 type | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Mean diameter (μm) | 100～200 | 100～160 | 140～200 | 80～150 |
| Viscosity number (ml/g) | 110～113 | 109 | 109 | 110 |
| Apparent density (g/mL) | 0.53～0.56 | 0.61 | 0.61 | 0.63 |
| The plasticizer absorption (g) of 100g resin | 21～23 | 13 | 12 | 6 |
| Fugitive constituent (%) | ＜ 0.4 | 0.31 | 0.32 | 0.3 |
| Whiteness (%) | 79～81 | 77 | 77 | 80 |
It can be seen that compared to general SG5 type Corvic, the chloroethene prepared by the present invention from data above
The index change that grades of the alkene-mean diameter of n-butyl acrylate copolymer resins, viscosity number, volatilization is inconspicuous, but apparent density is obvious
Higher 0.05～0.1g/mL, show that it has higher apparent density；The plasticizer absorption the most on the low side 10 of 100g resin～
15g, thus show copolymer resins and there is obvious internal plasticization；Butyl acrylate content is the copolymer resins of 5% simultaneously
Relatively content is that the oil absorbency of the copolymer resins of 3% is lower, shows the copolymer resins internal plasticization effect that butyl acrylate content is 5%
Fruit is more preferably.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (6)
1. the preparation method of a suspension method vinylchloride-acrylic acid N-butyl copolymer resins, it is characterised in that: include following step
Rapid:
(1) being separately added into polymeric kettle after pure water, Vinyl Chloride Monomer, dispersant, initiator A metering, controlling reaction temperature is 45
～70 DEG C, polymerization process starts water filling after starting, and polyreaction starts to 180min just adding acrylic acid the most continuously
Butyl ester, when polyreaction is carried out to 90min～120min, adds initiator B；
(2) after polyreaction 300min, adding terminator after pressure drop 0.05～0.15MPa, after stirring, discharging is to slurry
Groove, through stripping by the Vinyl Chloride Monomer desorption in copolymer resins, sends into drying system and is dried.
The preparation method of a kind of suspension method vinylchloride-acrylic acid N-butyl copolymer resins the most according to claim 1, it is special
Levy and be: pure water in step (1): 110～150 mass parts, Vinyl Chloride Monomer: 100 mass parts, dispersant: 0.07～0.1 mass
Part, initiator A: 0.08～0.11 mass parts, water filling: 25～50 mass parts, initiator B: 0.003～0.006 mass parts, propylene
Acid N-butyl: 3～5 mass parts.
The preparation method of a kind of suspension method vinylchloride-acrylic acid N-butyl copolymer resins the most according to claim 1 and 2,
It is characterized in that: described dispersant is selected from hydroxypropyl methyl cellulose, alcoholysis degree is 79～81 polyvinyl alcohol, alcoholysis degree are
The polyvinyl alcohol of 71.5～73.5, alcoholysis degree are that three kinds or four kinds in the polyvinyl alcohol of 45～51 are combined.
The preparation method of a kind of suspension method vinylchloride-acrylic acid N-butyl copolymer resins the most according to claim 1 and 2,
It is characterized in that: described initiator A be peroxy dicarbonate two (2-ethyl hexyl) ester, the two of cumyl peroxyneodecanoate
Plant mixing.
The preparation method of a kind of suspension method vinylchloride-acrylic acid N-butyl copolymer resins the most according to claim 1 and 2,
It is characterized in that: described initiator B is cumyl peroxyneodecanoate (CNP).
The preparation method of a kind of suspension method vinylchloride-acrylic acid N-butyl copolymer resins the most according to claim 1, it is special
Levy and be: the terminator described in step (2) be α-methyl styrene content be the aqueous solution of 12%.
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| CN201610688034.3A CN106279490A (en) | 2016-08-18 | 2016-08-18 | A kind of preparation method of suspension method vinyl chloride acrylic N-butyl copolymer resins |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082976A (en) * | 2017-05-04 | 2017-08-22 | 宜宾天原集团股份有限公司 | A kind of high-impact high fluidity PVC formulas and preparation method thereof |
| CN107082977A (en) * | 2017-05-04 | 2017-08-22 | 宜宾天原集团股份有限公司 | A kind of high-impact high fluidity PVC injected plastics materials formula and preparation method thereof |
| CN109053945A (en) * | 2018-07-18 | 2018-12-21 | 浙江威思康塑胶有限公司 | A kind of preparation method of acrylic acid modified active polyvinyl chloride through activity |
| CN109400784A (en) * | 2018-10-19 | 2019-03-01 | 新疆中泰化学股份有限公司 | Ultra low polymerization degree vinyl chloride-butyl acrylate copolymer resins and preparation method thereof |
| CN112125999A (en) * | 2020-09-19 | 2020-12-25 | 河北河汇新材料科技有限公司 | Preparation method of vinyl chloride and butyl acrylate suspension copolymer resin |
| CN112409543A (en) * | 2020-10-26 | 2021-02-26 | 安徽天辰化工股份有限公司 | Preparation method of vinyl chloride and acrylate copolymer emulsion |
| CN114395069A (en) * | 2021-12-21 | 2022-04-26 | 云南正邦科技有限公司 | Novel plasticizer-free soft PVC (polyvinyl chloride) and preparation method thereof |
| CN115926037A (en) * | 2022-12-16 | 2023-04-07 | 宜宾天原科创设计有限公司 | Preparation method of polyvinyl chloride resin special for PVC-O pipe and prepared polyvinyl chloride resin |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082976A (en) * | 2017-05-04 | 2017-08-22 | 宜宾天原集团股份有限公司 | A kind of high-impact high fluidity PVC formulas and preparation method thereof |
| CN107082977A (en) * | 2017-05-04 | 2017-08-22 | 宜宾天原集团股份有限公司 | A kind of high-impact high fluidity PVC injected plastics materials formula and preparation method thereof |
| CN107082976B (en) * | 2017-05-04 | 2019-08-06 | 宜宾天原集团股份有限公司 | A kind of high-impact high fluidity PVC formula and preparation method thereof |
| CN109053945A (en) * | 2018-07-18 | 2018-12-21 | 浙江威思康塑胶有限公司 | A kind of preparation method of acrylic acid modified active polyvinyl chloride through activity |
| CN109400784A (en) * | 2018-10-19 | 2019-03-01 | 新疆中泰化学股份有限公司 | Ultra low polymerization degree vinyl chloride-butyl acrylate copolymer resins and preparation method thereof |
| CN112125999A (en) * | 2020-09-19 | 2020-12-25 | 河北河汇新材料科技有限公司 | Preparation method of vinyl chloride and butyl acrylate suspension copolymer resin |
| CN112409543A (en) * | 2020-10-26 | 2021-02-26 | 安徽天辰化工股份有限公司 | Preparation method of vinyl chloride and acrylate copolymer emulsion |
| CN114395069A (en) * | 2021-12-21 | 2022-04-26 | 云南正邦科技有限公司 | Novel plasticizer-free soft PVC (polyvinyl chloride) and preparation method thereof |
| CN115926037A (en) * | 2022-12-16 | 2023-04-07 | 宜宾天原科创设计有限公司 | Preparation method of polyvinyl chloride resin special for PVC-O pipe and prepared polyvinyl chloride resin |
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