CN106008780A - Method for preparing shock-resistant vinyl chloride copolymer resin - Google Patents

Method for preparing shock-resistant vinyl chloride copolymer resin Download PDF

Info

Publication number
CN106008780A
CN106008780A CN201610412735.4A CN201610412735A CN106008780A CN 106008780 A CN106008780 A CN 106008780A CN 201610412735 A CN201610412735 A CN 201610412735A CN 106008780 A CN106008780 A CN 106008780A
Authority
CN
China
Prior art keywords
vinyl chloride
monomer
copolymer resin
reaction temperature
chloride copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610412735.4A
Other languages
Chinese (zh)
Other versions
CN106008780B (en
Inventor
周大胜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Kuayue Printing Co ltd
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201610412735.4A priority Critical patent/CN106008780B/en
Publication of CN106008780A publication Critical patent/CN106008780A/en
Application granted granted Critical
Publication of CN106008780B publication Critical patent/CN106008780B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention discloses a method for preparing shock-resistant vinyl chloride copolymer resin. A polymerization method is optimized by optimizing a polymerization monomer formula, a dispersing agent formula, polymerization reaction temperature and time, the charging mode and other factors influencing a polymerization reaction. A product processed through the vinyl chloride copolymer resin prepared through the method has excellent processability, barrier performance, fire resistance and shock resistance, is widely applied to the fields of the industries of buildings, packages, cars, food and the like, and has wide market prospects.

Description

A kind of preparation method of the vinyl chloride copolymer resin of resistance to impact
The present invention is application number: 2014108369832, the applying date: 2014-12-29, denomination of invention: The divisional application of the vinyl chloride copolymer resin planting resistance to impact and preparation method thereof.
Technical field
The present invention relates to a kind of vinyl chloride copolymer resin and preparation method thereof, particularly relate to a kind of resistance to impact The copolymer resin of vinyl chloride, vinylidene chloride, acrylate and maleic anhydride and preparation method thereof.
Background technology
Though polrvinyl chloride prepared at laboratory the most as far back as 1835, but because of poor heat stability, processing should With never breaking through.Arrived eighties of last century end of the twenties, occur in that of both break through: one is plasticising, Goodrich companies in 1933 have delivered the patent adding plasticizer；Another is copolymerization, and PVC is served structure Improve, be conducive to processing.The chloroethylene copolymer species produced in the world at present not less than dozens, kind board Number more.Poor due to the processing type of polrvinyl chloride, impact strength, dissolubility etc., can not meet some special Different purposes, the therefore new polrvinyl chloride kind of development.
VDC-VC copolymer resins from 1936 come out since, U.S. DOW, Japan Wu Yu, the Northeast electrification, Company's competitively Development and Production such as East Asia synthesis go out VDC-VC suspension copolymer resin.Domestic open from the eighties in 20th century Begin to study synthesis technique and the performance of VDC-VC copolymer resins, have accumulated certain theoretical basis and technology.Work Use free radical to suspend in industry and emulsion is polymerized VDC-VC polymer processed, mainly with VDC as main monomer, by React to monomer chain tra nsfer etc. in existing, cause the formation of unstable structure in polymer chain, the heat of polymer Less stable, affects processing characteristics.
US4983311A describes a kind of vinyl chloride copolymer, hydroxyl and two groups of carboxylic acid group by all mixing Liquid polymerization is simultaneously introduced in polymer adhesive.In being preferable to carry out one, vinyl chloride, glycerol monoallyl Ether, acetone, benzoyl peroxide first phthalein are added by fed-batch mode, and maleic acid, vinylidene chloride and methanol are logical Cross quantitative feeding mode to add.But owing to employing multi-solvents, the dependence to solvent causes environmental problem And add the cost of production.
US5912082A disclose a kind of to vinyl chloride or vinyl chloride and other mixture of vinyl monomer with contain Carboxylic monomer is polymerized, thus the method obtaining vinyl chloride copolymer.Hydroxyl monomer is by dihydroxy Base or polyhydroxy-alcohol part allylation obtain.This copolymer is prepared by suspension polymerization, hydroxyl There is the character substantially changing polymer, plasticizer absorption rate substantially increases and drying time significantly reduces. It addition, hydroxyl becomes the reflecting point of post-polymerization due to its polarity and activity.But owing to carboxylic monomer enters Having arrived polrvinyl chloride main chain, resin heat stability in the course of processing is inadequate, easily decomposes and makes goods variable color.
CN101386661A discloses the preparation method of a kind of polychloroethylene with high polymerization degree, vinyl chloride main monomer with Diallyl fumarate, DAIP and/or diallyl maleate comonomer use and suspend Copolymerization process obtains high polymerization degree vinyl chloride copolymer resin, employs the compound system of chain extender/chain-transferring agent Shorten the response time, solve polymeric reaction temperature difficulty control problem, and improve the processability of goods, Improve its mechanical property.But the method is faced with the difficult separation and recycling of monomer and resin, and cost produces Higher.
CN103265658A discloses the synthetic method of a kind of heat resistant type chloroethylene copolymer resin, uses emulsion to gather Conjunction method is by Vinyl Chloride Monomer and second comonomer or second comonomer and Third monomer, poly-under anaerobic airtight condition Closing reaction, polymerization temperature is 45-65 DEG C, when reaction temperature reaches set temperature value, starts to add initiator And, prepare copolymer emulsion, this LS is dried and i.e. prepares polyvinyl chloride copolymer.But the method is adopted The resin prepared with emulsion polymerization way is difficult to obtain controlled grain diameter and porosity, and molecular weight Distribution width.
Summary of the invention
Not enough for prior art, the present invention provides a kind of with vinyl chloride as main monomer, vinylidene chloride, propylene Acid esters and maleic anhydride monomer carry out resistance to impact vinyl chloride copolymer resin and the preparation thereof of modification by copolymerization Method.
To achieve the above object of the invention, the present invention provides the preparation of a kind of resistance to impact vinyl chloride copolymer resin Method, described copolymer resin is made up by suspension polymerisation of the raw material of following parts by weight: mix monomer 100 Part, dispersant 0.1-1 part, initiator 0.05-0.3 part, pH adjusting agent 0.1-2 part, chain-transferring agent 0.05-0.2 Part and deionized water 100-300 part；
Described mix monomer consists of the following components in percentage by weight: vinyl chloride 60-90%, vinylidene chloride 5-30%, acrylate 1-10% and maleic anhydride (MA) 1-5%；
Described dispersant is hydroxypropyl methyl cellulose and/or polyvinyl alcohol (PVA)；
Described initiator is azo compound or persulfate；
Described pH adjusting agent is hydrophosphate or bicarbonate；
Described chain-transferring agent is aliphatic mercaptan；
Described preparation method comprises the steps:
(1) under the protection of noble gas, Vinyl Chloride Monomer, dispersant, part initiator, pH are adjusted Joint agent and deionized water join reactor, pre-dispersed 20-30min under room temperature；
(2) heat up and control at reaction temperature 30-70 DEG C react 15-45min, then add vinylidene chloride and Crylic acid ester mixture monomer；
(3) after completing monomer interpolation, add residue initiator, control to react at reaction temperature 30-70 DEG C 15-30min；
(4) reactor temperature is warming up to 40-80 DEG C, drips maleic anhydride monomer；
(5) when polymerization pressure declines 0.1-0.3MPa, add chain-transferring agent, stop stirring, reduce Reaction temperature, residual gas in releasing reactor, discharging；
(6) discharging is through filtering, washing and dried, obtains vinyl chloride copolymer resin；
Described acrylate is selected from acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate and acrylic acid-2-ethyl One or more in own ester；
Described dispersant consists of the following components in percentage by weight: polyvinyl alcohol (PVA) 20-80% and hydroxyl Propyl methocel 20-80%.
The present invention is by aggregation Monomer Formations, dispersant formulation, polymeric reaction temperature and time, charging Modes etc. affect the factor of polyreaction, optimize polymerization, are obtained by the preparation method of the present invention Vinyl chloride copolymer resin product, has relatively high resin particle diameter, owing to introducing vinylidene chloride, no in polymerization Satisfied fatty acid and maleic anhydride so that the flexibility of molecule segment in whole molecular structure, can be strengthened, The property that resin is excellent can be given, as reduce resin melt temperature, improve resin heat stability, Strengthen the impact resistance of goods, be widely used in the fields such as building, packaging, automobile, food service industry, have relatively Good market prospect.Compared with prior art, the method have the advantages that
1, by introducing vinylidene chloride, unsaturated fatty acid and maleic anhydride on polrvinyl chloride main chain, Optimizing the chain structure of main chain, the intensity of vinyl chloride copolymer resin particle is higher, the most broken, uses the longevity Life is long, and its fabricated product has excellent impact resistance, the transparency, barrier and anti-flammability；
2, by adjusting, improving dispersant dosage and coupling, bulky grain and little granule, holding can be eliminated Particle diameter compares concentration, and grain form is regular, fine and close, has relatively low porosity and relatively high apparent density, particle diameter Resin ratio between 0.2-0.25mm is more than 85%, and apparent density is at 0.55-0.75g/ml.
3, introduce different monomers at different polymerization stages, be conducive to effectively controlling polymerization rate, copolymer Composition and the molecular weight of copolymer, form the relatively uniform vinyl chloride copolymer of composition；
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to this A little detailed description of the invention.One skilled in the art would recognize that and present invention encompasses Claims scope Interior potentially included all alternatives, improvement project and equivalents.
Embodiment 1
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 2688g Vinyl Chloride Monomer, 18g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C Lower reaction 30min, then adds 148g vinylidene chloride monomer and 93g n-butyl acrylate monomer, completes list After body adds, then add 2g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 60g Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor Gas, discharging and through filter, washing and dried, obtain 2535g vinyl chloride copolymer resin.Through unit Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin Dividing content is 89.2%；Molar content shared by vinylidene chloride construction unit is 5.2%；N-butyl acrylate Molar content shared by construction unit is 3.4%；Molar content shared by maleic anhydride construction unit It is 2.2%.
Polymer data: resin particle diameter 213 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.68g/cm3, porosity is 55%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 67.3MPa, shock strength (GB/T 1843-1996) it is 28.3KJ/m2, specifically it is shown in Table 1.
Embodiment 2
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 2412g Vinyl Chloride Monomer, 16g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C Lower reaction 30min, then adds 296g vinylidene chloride monomer and 242g n-butyl acrylate monomer, completes list After body adds, then add 4g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 60g Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor Gas, discharging and through filter, washing and dried, obtain 2619g vinyl chloride copolymer resin.Through unit Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin Dividing content is 78.4%；Molar content shared by vinylidene chloride construction unit is 10.5%；N-butyl acrylate Molar content shared by construction unit is 9.0%；Molar content shared by maleic anhydride construction unit It is 2.1%.
Polymer data: resin particle diameter 223 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.62g/cm3, porosity is 49%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 65.3MPa, shock strength (GB/T 1843-1996) it is 31.4KJ/m2, specifically it is shown in Table 1.
Embodiment 3
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 2088g Vinyl Chloride Monomer, 14g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C Lower reaction 30min, then adds 603g vinylidene chloride monomer and 153g n-butyl acrylate monomer, completes list After body adds, then add 6g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 146g Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor Gas, discharging and through filter, washing and dried, obtain 2608g vinyl chloride copolymer resin.Through unit Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin Dividing content is 68.8%；Molar content shared by vinylidene chloride construction unit is 20.4%；N-butyl acrylate Molar content shared by construction unit is 5.5%；Molar content shared by maleic anhydride construction unit It is 5.3%, is specifically shown in Table 1.
Polymer data: resin particle diameter 234 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.58g/cm3, porosity is 45%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 59.7MPa, shock strength (GB/T 1843-1996) it is 34.8KJ/m2, specifically it is shown in Table 1.
Embodiment 4
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 1804g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C Lower reaction 30min, then adds 743g vinylidene chloride monomer and 303g n-butyl acrylate monomer, completes list After body adds, then add 8g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 152g Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor Gas, discharging and through filter, washing and dried, obtain 2643g vinyl chloride copolymer resin.Through unit Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin Dividing content is 58.0%；Molar content shared by vinylidene chloride construction unit is 25.6%；N-butyl acrylate Molar content shared by construction unit is 10.9%；Molar content shared by maleic anhydride construction unit It is 5.5%.
Polymer data: resin particle diameter 252 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.56g/cm3, porosity is 42%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 58.7MPa, shock strength (GB/T 1843-1996) it is 35.2KJ/m2, specifically it is shown in Table 1.
Embodiment 5
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 2408g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate, 125g hydroxypropyl methyl cellulose (hydroxyl Propyl group content is 6.3mol%) and 60g polyvinyl alcohol (alcoholysis degree is 65%), it is stirred at room temperature pre-dispersed 25min, heats up and controls to react at reaction temperature 55 DEG C 30min, then adding 296g vinylidene chloride monomer With 242g n-butyl acrylate monomer, after completing monomer interpolation, then add 4g sodium peroxydisulfate and control reaction React 20min, then dropping 60g maleic anhydride monomer at temperature 55 DEG C, heat up and control reaction temperature Spend 60 DEG C, when polymerization pressure declines 0.2MPa, add 18g n-dodecyl mercaptan and stop stirring, Reduce reaction temperature, residual gas in releasing reactor, discharging and through filter, washing and dried, To 2635g vinyl chloride copolymer resin.Vinyl chloride copolymer is confirmed through elementary analysis, nuclear-magnetism, infrared analysis In resin, molar content shared by vinyl chloride construction unit is 77.9%；Shared mole of vinylidene chloride construction unit Percentage composition is 11.0%；Molar content shared by n-butyl acrylate construction unit is 8.9%；Maleic Molar content shared by dicarboxylic anhydride construction unit is 2.2%.
Polymer data: resin particle diameter 219 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.65g/cm3, porosity is 47%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 66.1MPa, shock strength (GB/T 1843-1996) it is 32.4KJ/m2, specifically it is shown in Table 1.
Embodiment 6
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 2415g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate, 95g hydroxypropyl methyl cellulose (hydroxyl Propyl group content is 6.3mol%) and 90g polyvinyl alcohol (alcoholysis degree is 65%), it is stirred at room temperature pre-dispersed 25min, heats up and controls to react at reaction temperature 55 DEG C 30min, then adding 296g vinylidene chloride monomer With 242g n-butyl acrylate monomer, after completing monomer interpolation, then add 4g sodium peroxydisulfate and control reaction React 20min, then dropping 60g maleic anhydride monomer at temperature 55 DEG C, heat up and control reaction temperature Spend 60 DEG C, when polymerization pressure declines 0.2MPa, add 18g n-dodecyl mercaptan and stop stirring, Reduce reaction temperature, residual gas in releasing reactor, discharging and through filter, washing and dried, To 2642g vinyl chloride copolymer resin.Vinyl chloride copolymer is confirmed through elementary analysis, nuclear-magnetism, infrared analysis In resin, molar content shared by vinyl chloride construction unit is 78.0%；Shared mole of vinylidene chloride construction unit Percentage composition is 10.8%；Molar content shared by n-butyl acrylate construction unit is 9.0%；Maleic Molar content shared by dicarboxylic anhydride construction unit is 2.2%.
Polymer data: resin particle diameter 216 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.73g/cm3, porosity is 44%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 66.8MPa, shock strength (GB/T 1843-1996) it is 34.5KJ/m2, specifically it is shown in Table 1.
Embodiment 7
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 2407g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate, 60g hydroxypropyl methyl cellulose (hydroxyl Propyl group content is 6.3mol%) and 125g polyvinyl alcohol (alcoholysis degree is 65%), it is stirred at room temperature pre-point Dissipate 25min, heat up and control to react at reaction temperature 55 DEG C 30min, then adding 296g vinylidene chloride list Body and 242g n-butyl acrylate monomer, after completing monomer interpolation, then add 4g sodium peroxydisulfate and control anti- Answer reaction 20min at temperature 55 DEG C, then dropping 60g maleic anhydride monomer, heat up and control reaction Temperature 60 C, when polymerization pressure declines 0.2MPa, adds 18g n-dodecyl mercaptan and stops stirring Mix, reduce reaction temperature, residual gas in releasing reactor, discharging and through filter, washing and dried, Obtain 2624g vinyl chloride copolymer resin.Chloroethylene copolymer is confirmed through elementary analysis, nuclear-magnetism, infrared analysis In resin, molar content shared by vinyl chloride construction unit is 77.8%；Rub shared by vinylidene chloride construction unit Your percentage composition is 11.0%；Molar content shared by n-butyl acrylate construction unit is 9.1%；Along fourth Molar content shared by enedioic acid acid anhydride construction unit is 2.1%.
Polymer data: resin particle diameter 217 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.68g/cm3, porosity is 46%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 65.9MPa, shock strength (GB/T 1843-1996) it is 31.0KJ/m2, specifically it is shown in Table 1.
Embodiment 8
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water, 2395g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g 2,2'-Azobis(2,4-dimethylvaleronitrile), 60g hydroxypropyl methyl cellulose (hydroxypropyl content is 6.3mol%) and 125g polyvinyl alcohol (alcoholysis degree is 65%), be stirred at room temperature Pre-dispersed 25min, heats up and controls to react at reaction temperature 55 DEG C 30min, then adding the inclined chloroethene of 296g Alkene monomer and 241g acrylic acid-2-ethyl caproite monomer, after completing monomer interpolation, then it is different to add 4g azo two Heptonitrile also controls to react at reaction temperature 55 DEG C 20min, then dropping 60g maleic anhydride monomer, rises Temperature also controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa, adds 18g dodecyl Mercaptan also stops stirring, reduces reaction temperature, residual gas in releasing reactor, discharging through filtering, washing Wash and dried, obtain 2648g vinyl chloride copolymer resin.Through elementary analysis, nuclear-magnetism, infrared analysis Confirm that in vinyl chloride copolymer resin, molar content shared by vinyl chloride construction unit is 78.1%；Vinylidene chloride Molar content shared by construction unit is 10.9%；Molar content shared by n-butyl acrylate construction unit It is 9.0%；Molar content shared by maleic anhydride construction unit is 2.0%.
Polymer data: resin particle diameter 235 μm that Coulter particle size analyzer measures；AutoPore-IV The resin apparent density that-9510 mercury injection apparatuses measure is 0.75g/cm3, porosity is 42%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 63.2MPa, shock strength (GB/T 1843-1996) it is 38.7KJ/m2, specifically it is shown in Table 1.
Table 1: vinyl chloride copolymer resin Performance comparision prepared by embodiment 1-8
Knowable to table 1 data, the present invention is by introducing vinylidene chloride, unsaturated lipid on polrvinyl chloride main chain Fat acid and maleic anhydride, and adjust whole, improve dispersant dosage and vinyl chloride that coupling prepares altogether Copolymer resin, grain form is regular, fine and close, has relatively low porosity and relatively high apparent density, and it processes system Product possess excellent tensile property and erosion-resisting characteristics.

Claims (1)

1. the preparation method of the vinyl chloride copolymer resin of a resistance to impact, it is characterised in that
Described copolymer resin is made up by suspension polymerisation of the raw material of following parts by weight: mix monomer 100 parts, Dispersant 0.1-1 part, initiator 0.05-0.3 part, pH adjusting agent 0.1-2 part, chain-transferring agent 0.05-0.2 part With deionized water 100-300 part；
Described mix monomer consists of the following components in percentage by weight: vinyl chloride 60-90%, vinylidene chloride 5-30%, acrylate 1-10% and maleic anhydride (MA) 1-5%；
Described dispersant is hydroxypropyl methyl cellulose and/or polyvinyl alcohol (PVA)；
Described initiator is azo compound or persulfate；
Described pH adjusting agent is hydrophosphate or bicarbonate；
Described chain-transferring agent is aliphatic mercaptan；
Described method comprises the steps:
(1) under the protection of noble gas, by Vinyl Chloride Monomer, dispersant, part initiator, pH regulator Agent and deionized water join reactor, pre-dispersed 20-30min under room temperature；
(2) heat up and control to react at reaction temperature 30-70 DEG C 15-45min, then adding vinylidene chloride and third Olefin(e) acid ester mix monomer；
(3) after completing monomer interpolation, add residue initiator, control to react at reaction temperature 30-70 DEG C 15-30min；
(4) reactor temperature is warming up to 40-80 DEG C, drips maleic anhydride monomer；
(5) when polymerization pressure declines 0.1-0.3MPa, add chain-transferring agent, stop stirring, reduce Reaction temperature, residual gas in releasing reactor, discharging；
(6) discharging is through filtering, washing and dried, obtains vinyl chloride copolymer resin；
Described acrylate is selected from acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate and acrylic acid-2-ethyl One or more in own ester；
Described dispersant consists of the following components in percentage by weight: polyvinyl alcohol (PVA) 20-80% and hydroxypropyl Ylmethyl cellulose 20-80%.
CN201610412735.4A 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance Expired - Fee Related CN106008780B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610412735.4A CN106008780B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610412735.4A CN106008780B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
CN201410836983.2A CN104448092B (en) 2014-12-29 2014-12-29 Preparation method of impact-resistant chloroethylene copolymer resin

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201410836983.2A Division CN104448092B (en) 2014-12-29 2014-12-29 Preparation method of impact-resistant chloroethylene copolymer resin

Publications (2)

Publication Number Publication Date
CN106008780A true CN106008780A (en) 2016-10-12
CN106008780B CN106008780B (en) 2017-11-17

Family

ID=52894891

Family Applications (5)

Application Number Title Priority Date Filing Date
CN201610412284.4A Expired - Fee Related CN105859943B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
CN201610412730.1A Expired - Fee Related CN105924559B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
CN201610412735.4A Expired - Fee Related CN106008780B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
CN201610414680.0A Active CN105968246B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
CN201410836983.2A Expired - Fee Related CN104448092B (en) 2014-12-29 2014-12-29 Preparation method of impact-resistant chloroethylene copolymer resin

Family Applications Before (2)

Application Number Title Priority Date Filing Date
CN201610412284.4A Expired - Fee Related CN105859943B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
CN201610412730.1A Expired - Fee Related CN105924559B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance

Family Applications After (2)

Application Number Title Priority Date Filing Date
CN201610414680.0A Active CN105968246B (en) 2014-12-29 2014-12-29 A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
CN201410836983.2A Expired - Fee Related CN104448092B (en) 2014-12-29 2014-12-29 Preparation method of impact-resistant chloroethylene copolymer resin

Country Status (1)

Country Link
CN (5) CN105859943B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108084318A (en) * 2017-12-28 2018-05-29 宁波俐辰新能源有限公司 A kind of nuisanceless flame-resistant high-temperature-resistant polyvinyl chloride and its manufacturing method
KR102251268B1 (en) * 2018-04-30 2021-05-12 주식회사 엘지화학 Vinyl chloride polymer and preparation method thereof
CN109369839B (en) * 2018-09-21 2020-12-29 无锡洪汇新材料科技股份有限公司 Self-crosslinking vinyl chloride copolymer emulsion and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030162927A1 (en) * 2002-02-26 2003-08-28 Shin-Etsu Chemical Co., Ltd. Method of producing a vinyl chloride-based polymer
CN101314627A (en) * 2008-06-04 2008-12-03 中国农业大学 Film-forming agent for seed clothing sheet and preparation method thereof
CN101367898A (en) * 2008-08-27 2009-02-18 浙江巨化股份有限公司电化厂 PVDC copolymerization emulsion, preparation and uses thereof
CN102459372A (en) * 2009-05-15 2012-05-16 阿肯马法国公司 Method for preparing a suspension of pvc grafted onto an elastomer
CN102850867A (en) * 2012-09-04 2013-01-02 海南必凯水性涂料有限公司 Heat-seal polyvinylidene chloride emulsion used for coating, and preparation method thereof
CN103467664A (en) * 2013-09-13 2013-12-25 四川凯本新材料科技有限公司 Preparation method of flame-retardant, impact-resistant and high-fluidity chloroethylene-based special resin

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1064848A (en) * 1962-11-17 1967-04-12 Kureha Chemical Ind Co Ltd Method for the production of vinyl resins
GB1385326A (en) * 1971-09-20 1975-02-26 Bp Chem Int Ltd Co-polymerisation process
JPS5358592A (en) * 1976-11-09 1978-05-26 Kureha Chem Ind Co Ltd Preparation of vinylidene chloride-vinyl chloride copolymer
JPS6295306A (en) * 1985-10-22 1987-05-01 Toagosei Chem Ind Co Ltd Production of vinylidene chloride copolymer
US5294684A (en) * 1990-05-22 1994-03-15 Shin-Etsu Chemical Co., Ltd. Process for producing vinyl chloride resin
JPH0493301A (en) * 1990-08-10 1992-03-26 Kuraray Co Ltd Dispersing agent and dispersion stabilizer for suspension polymerization of vinyl monomer
JP2872472B2 (en) * 1991-12-27 1999-03-17 三菱重工業株式会社 Conductive paint for prevention of marine organism adhesion
EP0633273A1 (en) * 1993-07-05 1995-01-11 Shin-Etsu Chemical Co., Ltd. Process for producing vinyl chloride polymers
JP5351023B2 (en) * 2006-08-25 2013-11-27 クラリアント ファイナンス （ビーブイアイ） リミティド Oil repellency, water repellency and soil repellency perfluoroalkylethyl methacrylate copolymer
CN103059192B (en) * 2012-12-26 2015-04-22 海南必凯水性涂料有限公司 Polyvinyl dichloride (PVDC) latex used for interior and exterior wall coating materials and preparation method thereof and application thereof
CN103193918A (en) * 2013-05-06 2013-07-10 南通瑞普埃尔生物工程有限公司 Vinyl chloride-vinylidene chloride (VDC)/acrylic acid (AA)/methyl methacrylate (MMA)/acrylonitrile (AN) copolymerized polyvinyl dichloride (PVDC) emulsion and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030162927A1 (en) * 2002-02-26 2003-08-28 Shin-Etsu Chemical Co., Ltd. Method of producing a vinyl chloride-based polymer
CN101314627A (en) * 2008-06-04 2008-12-03 中国农业大学 Film-forming agent for seed clothing sheet and preparation method thereof
CN101367898A (en) * 2008-08-27 2009-02-18 浙江巨化股份有限公司电化厂 PVDC copolymerization emulsion, preparation and uses thereof
CN102459372A (en) * 2009-05-15 2012-05-16 阿肯马法国公司 Method for preparing a suspension of pvc grafted onto an elastomer
CN102850867A (en) * 2012-09-04 2013-01-02 海南必凯水性涂料有限公司 Heat-seal polyvinylidene chloride emulsion used for coating, and preparation method thereof
CN103467664A (en) * 2013-09-13 2013-12-25 四川凯本新材料科技有限公司 Preparation method of flame-retardant, impact-resistant and high-fluidity chloroethylene-based special resin

Also Published As

Publication number Publication date
CN105968246A (en) 2016-09-28
CN104448092B (en) 2017-02-22
CN105968246B (en) 2018-03-20
CN104448092A (en) 2015-03-25
CN105859943B (en) 2017-12-19
CN105924559A (en) 2016-09-07
CN105924559B (en) 2017-12-08
CN105859943A (en) 2016-08-17
CN106008780B (en) 2017-11-17

Similar Documents

Publication Publication Date Title
KR950006267B1 (en) Polymer emulsion containing an interpenetrating polymer network
CN101367898B (en) PVDC copolymerization emulsion, preparation and uses thereof
CN106008780A (en) Method for preparing shock-resistant vinyl chloride copolymer resin
CN109054570B (en) Environment-friendly high-strength elastic coating and preparation method thereof
CN103665241B (en) A kind of Cationic ethylene-vinyl acetate copolymer emulsion and production method thereof
CN102030857A (en) Vinyl acetate-ethylene copolymer emulsion as electrostatic spinning adhesive and synthesis method thereof
CN113717309B (en) Processing modified additive and preparation method thereof
JP2007084835A (en) Method for producing re-dispersion plastic powder
CN104558320B (en) Polyvinyl acetate emulsion
CN103626910A (en) Solid ethylene-vinyl acetate copolymer and preparation method thereof
CN107488246A (en) A kind of micro- tertiary acrylate and vinyl acetate emulsion of crosslinking and preparation method and application
CN103739769A (en) Method for preparing novel hydrophobic association type polymer surfactant
CN104761673B (en) A kind of carbomer and preparation method thereof
CN103588413B (en) A kind of polyethers cross-linking type cement water reducing agent and preparation method thereof and application
CN101326205B (en) Polyvinylester and poly(meth)acrylate solid resins having high polydispersity
CN104945576A (en) Preparation method, products and application of high efficiency slushing agent
CN106479407A (en) A kind of paper-plastic stick adhesive and preparation method thereof
CN111333765B (en) Vinyl chloride-vinyl acetate-acrylic acid-2-ethylhexyl ester copolymer resin and preparation method thereof
CN104628962A (en) Method for synthesizing cement disperser from acrylamide-fatty acid vinyl ester graft copolymer
JP5855754B2 (en) Vinyl acetate / vinyl 3,5,5-trimethylhexanoate copolymer binder resin
CN103923276A (en) Method for synthesizing polyether-type polycarboxylate water reducer
CN106883358A (en) A kind of four arm star polycarboxylic acid super-plasticizers and its preparation method and application
CN102264780A (en) Alkyl methacrylate/alkyl acrylate copolymers used as sizing for reinforcing fiber
CN110272516A (en) A kind of modified crosslinked pvc resin and preparation method thereof
CN110105500A (en) A kind of preparation method of super-hydrophobic paper surface treating agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20171023

Address after: 325000 Zhejiang province Wenzhou city Cangnan County Longgang Zhenlong gold road Shuang Gui Village

Applicant after: ZHEJIANG KUAYUE PRINTING Co.,Ltd.

Address before: Yuyao City, Zhejiang province 315400 Ningbo Yangming Street Road No. 42 South

Applicant before: Zhou Dasheng

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20171117

Termination date: 20211229

CF01 Termination of patent right due to non-payment of annual fee