A kind of preparation method of the vinyl chloride copolymer resin of impact resistance
The present invention is application number:2014108369832, the applying date:2014-12-29, denomination of invention:A kind of impact resistance
Vinyl chloride copolymer resin and preparation method thereof divisional application.
Technical field
The present invention relates to a kind of vinyl chloride copolymer resin and preparation method thereof, more particularly to a kind of chloroethene of impact resistance
Alkene, vinylidene chloride, the copolymer resin and preparation method thereof of acrylate and maleic anhydride.
Background technology
Though polyvinyl chloride just prepared in laboratory early in 1835, because heat endurance is poor, processed and applied is always
Do not break through.To the last century 20's Mo, there is both sides and break through:First, plasticising, Goodrich companies in 1933
The patent of addition plasticizer is delivered;Another is copolymerization, and structure improvement is served to PVC, is advantageous to process.Give birth in the world at present
The chloroethylene copolymer species of production not less than dozens, the kind trade mark is more.Due to the processing type of polyvinyl chloride, impact strength, molten
Solution property etc. is poor, can not meet some specific uses, therefore continued to develop new polyvinyl chloride kind.
VDC-VC copolymer resinses are since 1936 come out, the public affairs such as U.S. DOW, Japanese Wu Yu, Northeast electrification, East Asia synthesis
Competitively Development and Production goes out VDC-VC suspension copolymer resins for department.The domestic VDC-VC copolymer resinses that begun one's study from the 1980s
Synthesis technique and performance, it have accumulated certain theoretical foundation and technology.Industrially suspended and emulsion polymerization system using free radical
VDC-VC polymer, mainly using VDC as main monomer, react, cause unstable in polymer chain due to existing to monomer chain tra nsfer etc.
Determine the formation of structure, the heat endurance of polymer is poor, influences processing characteristics.
US4983311A describes a kind of vinyl chloride copolymer, and two groups of hydroxyl and carboxylic acid group pass through homogeneous solution polymerization
Method is added in polymer adhesive simultaneously.In one is preferable to carry out, vinyl chloride, allylin, acetone, benzoyl peroxide first
Phthalein is added by fed-batch mode, and maleic acid, vinylidene chloride and methanol are added by quantitative feeding mode.But due to using
Multi-solvents, the dependence to solvent cause environmental problem and add the cost of production.
US5912082A discloses a kind of to vinyl chloride or vinyl chloride and other mixture of vinyl monomer and hydroxyl list
Body is polymerize, so as to obtain the method for vinyl chloride copolymer.Hydroxyl monomer is by dihydroxy or polyhydroxy-alcohol part
What allylation obtained.The copolymer is prepared by suspension polymerization, and the presence of hydroxyl substantially changes the property of polymer,
Plasticizer absorption rate substantially increases and drying time significantly reduces.In addition, hydroxyl polymerize after turning into due to its polarity and activity it is anti-
The reflecting point answered.But because carboxylic monomer has entered polyvinyl chloride main chain, heat endurance is inadequate in process for resin, hold
Easily decomposing makes product change colour.
CN101386661A discloses a kind of preparation method of polychloroethylene with high polymerization degree, vinyl chloride main monomer and fumaric acid
Diallyl, DAIP and/or diallyl maleate comonomer obtain height using suspension copolymerization method
Degree of polymerization vinyl chloride copolymer resin, use the compound system of chain extender/chain-transferring agent to shorten the reaction time, solved polymerization
Reaction temperature difficulty control problem, and the processability of product is improved, improve its mechanical property.But this method is faced with monomer
With the difficult separation and recycling of resin, and cost production it is higher.
CN103265658A discloses a kind of synthetic method of heat resistant type chloroethylene copolymer resin, using emulsion polymerisation process
By VCM and second comonomer or second comonomer and Third monomer, in anaerobic polymerisation under confined conditions, polymerization temperature
For 45-65 DEG C, when reaction temperature reaches set temperature value, start add initiator and, be made copolymer emulsion, by this emulsion
Polyvinyl chloride copolymer is made in spray drying.But the resin that this method is prepared using emulsion polymerization way is difficult to acquisition can
The grain diameter and porosity of control, and molecular weight distribution is wide.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides one kind using vinyl chloride as main monomer, vinylidene chloride, acrylate and suitable
Butene dioic acid anhydride monomer carries out impact resistance vinyl chloride copolymer resin of modification by copolymerization and preparation method thereof.
To achieve the above object of the invention, the present invention provides a kind of preparation method of impact resistance vinyl chloride copolymer resin,
The copolymer resin is made up of the raw material of following parts by weight of suspension polymerisation:100 parts of mix monomer, dispersant 0.1-1
Part, initiator 0.05-0.3 parts, pH adjusting agent 0.1-2 parts, chain-transferring agent 0.05-0.2 parts and deionized water 100-300 parts;
The 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%;
The dispersant is hydroxypropyl methyl cellulose and/or polyvinyl alcohol (PVA);
The initiator is azo compound or persulfate;
The pH adjusting agent is hydrophosphate or bicarbonate;
The chain-transferring agent is aliphatic mercaptan;
The preparation method comprises the following steps:
(1) under the protection of inert gas, by VCM, dispersant, part initiator, pH adjusting agent and deionization
Water is added to reactor, at room temperature pre-dispersed 20-30min;
(2) 15-45min is reacted at 30-70 DEG C of heating and controlling reaction temperature, then adds vinylidene chloride and acrylate
Mix monomer;
(3) after completing monomer addition, remaining initiator is added, reacts 15-30min at 30-70 DEG C of controlling reaction temperature;
(4) reactor temperature is warming up to 40-80 DEG C, and maleic anhydride monomer is added dropwise;
(5) when polymerization pressure declines 0.1-0.3MPa, chain-transferring agent is added, stops stirring, reduces reaction temperature,
Residual gas in releasing reactor, discharging;
(6) discharge filtered, washing and drying process, obtains vinyl chloride copolymer resin;
The dispersant consists of the following components in percentage by weight:Polyvinyl alcohol (PVA) 20-80% and hydroxypropyl methyl
Cellulose 20-80%;
The alcoholysis degree of the polyvinyl alcohol (PVA) is 69-89mol%, and the hydroxypropyl of the hydroxypropyl methyl cellulose contains
Measure as 4-12mol%.
The present invention is by optimizing the shadows such as polymerized monomer formula, dispersant formulation, polymeric reaction temperature and time, feed way
The factor of polymerisation is rung, optimizes polymerization, the vinyl chloride copolymer resin obtained by the preparation method of the present invention produces
Product, have compared with high resin particle diameter, due to introducing vinylidene chloride, unrighted acid and maleic anhydride in polymerization so that
The flexibility of molecule segment can be strengthened in whole molecular structure, can assign resin excellent property, as reduced resin
Melting temperature, heat endurance, the impact resistance of enhanced article for improving resin, are widely used in building, packaging, automobile, food row
The fields such as industry, there are preferable market prospects.Compared with prior art, the invention has the advantages that:
1st, by introducing vinylidene chloride, unrighted acid and maleic anhydride on polyvinyl chloride main chain, optimize
The chain structure of main chain, the intensity of vinyl chloride copolymer resin particle is higher, non-breakable, service life length, its fabricated product tool
There are excellent impact resistance, the transparency, barrier and anti-flammability;
2nd, by adjusting, improving dispersant dosage and matching, bulky grain and little particle can be eliminated, keeps particle footpath to compare
Concentrate, grain form is regular, fine and close, has relatively low porosity and compared with high apparent density, tree of the particle diameter between 0.2-0.25mm
Fat ratio is more than 85%, and apparent density is in 0.55-0.75g/ml.
3rd, different monomers are introduced in different polymerization stages, is advantageous to effectively control polymerization rate, the composition of copolymer
And the molecular weight of copolymer, formed and form relatively uniform vinyl chloride copolymer;
Embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalents.
Embodiment 1
Under the protection of inert gas, 6L high purity deionized waters, 2688g chlorine are added into 10L stainless steel autoclaves
Vinyl monomer, 18g sodium peroxydisulfates, 28g sodium acid carbonates and 185g hydroxypropyl methyl celluloses (hydroxypropyl content 6.3mol%),
Pre-dispersed 25min is stirred at room temperature, heats up and reacts 30min at 55 DEG C of controlling reaction temperature, then add the inclined chloroethenes of 148g
Alkene monomer and 93g n-butyl acrylate monomers, after completing monomer addition, then add 55 DEG C of 2g sodium peroxydisulfates and controlling reaction temperature
Lower reaction 20min, 60g maleic anhydride monomers are then added dropwise, heat up simultaneously 60 DEG C of controlling reaction temperature, works as polymerization pressure
When declining 0.2MPa, addition 18g n-dodecyl mercaptans simultaneously stop stirring, reduction reaction temperature, remaining gas in releasing reactor
Body, discharging and filtered, washing and drying process, obtain 2535g vinyl chloride copolymer resins.Through elementary analysis, nuclear-magnetism, infrared
Analysis confirms that molar content shared by vinyl chloride construction unit is 89.2% in vinyl chloride copolymer resin;Vinylidene chloride structure
Molar content shared by unit is 5.2%;Molar content shared by n-butyl acrylate construction unit is 3.4%;Along fourth
Molar content shared by enedioic acid acid anhydride construction unit is 2.2%.
Polymer data:213 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.68g/cm3, porosity 55%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 67.3MPa, shock strength (GB/T1843-
1996) it is 28.3KJ/m2, specifically it is shown in Table 1.
Embodiment 2
Under the protection of inert gas, 6L high purity deionized waters, 2412g chlorine are added into 10L stainless steel autoclaves
Vinyl monomer, 16g sodium peroxydisulfates, 28g sodium acid carbonates and 185g hydroxypropyl methyl celluloses (hydroxypropyl content 6.3mol%),
Pre-dispersed 25min is stirred at room temperature, heats up and reacts 30min at 55 DEG C of controlling reaction temperature, then add the inclined chloroethenes of 296g
Alkene monomer and 242g n-butyl acrylate monomers, after completing monomer addition, then add 4g sodium peroxydisulfates and controlling reaction temperature 55
20min is reacted at DEG C, 60g maleic anhydride monomers are then added dropwise, heat up simultaneously 60 DEG C of controlling reaction temperature, when polymerisation pressure
When power declines 0.2MPa, addition 18g n-dodecyl mercaptans simultaneously stop stirring, reduction reaction temperature, remaining in releasing reactor
Gas, discharging and filtered, washing and drying process, obtain 2619g vinyl chloride copolymer resins.Through elementary analysis, nuclear-magnetism, red
Outer analysis confirm that molar content shared by vinyl chloride construction unit is 78.4% in vinyl chloride copolymer resin;Vinylidene chloride knot
Molar content shared by structure unit is 10.5%;Molar content shared by n-butyl acrylate construction unit is 9.0%;It is suitable
Molar content shared by anhydride maleique construction unit is 2.1%.
Polymer data:223 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.62g/cm3, porosity 49%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 65.3MPa, shock strength (GB/T1843-
1996) it is 31.4KJ/m2, specifically it is shown in Table 1.
Embodiment 3
Under the protection of inert gas, 6L high purity deionized waters, 2088g chlorine are added into 10L stainless steel autoclaves
Vinyl monomer, 14g sodium peroxydisulfates, 28g sodium acid carbonates and 185g hydroxypropyl methyl celluloses (hydroxypropyl content 6.3mol%),
Pre-dispersed 25min is stirred at room temperature, heats up and reacts 30min at 55 DEG C of controlling reaction temperature, then add the inclined chloroethenes of 603g
Alkene monomer and 153g n-butyl acrylate monomers, after completing monomer addition, then add 6g sodium peroxydisulfates and controlling reaction temperature 55
20min is reacted at DEG C, 146g maleic anhydride monomers are then added dropwise, heat up simultaneously 60 DEG C of controlling reaction temperature, works as polymerisation
When pressure declines 0.2MPa, add 18g n-dodecyl mercaptans and stop stirring, reduce reaction temperature, remained in releasing reactor
Residual air body, discharging and filtered, washing and drying process, obtain 2608g vinyl chloride copolymer resins.Through elementary analysis, nuclear-magnetism,
Infrared analysis confirms that molar content shared by vinyl chloride construction unit is 68.8% in vinyl chloride copolymer resin;Vinylidene chloride
Molar content shared by construction unit is 20.4%;Molar content shared by n-butyl acrylate construction unit is 5.5%;
Molar content shared by maleic anhydride construction unit is 5.3%, is specifically shown in Table 1.
Polymer data:234 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.58g/cm3, porosity 45%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 59.7MPa, shock strength (GB/T1843-
1996) it is 34.8KJ/m2, specifically it is shown in Table 1.
Embodiment 4
Under the protection of inert gas, 6L high purity deionized waters, 1804g chlorine are added into 10L stainless steel autoclaves
Vinyl monomer, 12g sodium peroxydisulfates, 28g sodium acid carbonates and 185g hydroxypropyl methyl celluloses (hydroxypropyl content 6.3mol%),
Pre-dispersed 25min is stirred at room temperature, heats up and reacts 30min at 55 DEG C of controlling reaction temperature, then add the inclined chloroethenes of 743g
Alkene monomer and 303g n-butyl acrylate monomers, after completing monomer addition, then add 8g sodium peroxydisulfates and controlling reaction temperature 55
20min is reacted at DEG C, 152g maleic anhydride monomers are then added dropwise, heat up simultaneously 60 DEG C of controlling reaction temperature, works as polymerisation
When pressure declines 0.2MPa, add 18g n-dodecyl mercaptans and stop stirring, reduce reaction temperature, remained in releasing reactor
Residual air body, discharging and filtered, washing and drying process, obtain 2643g vinyl chloride copolymer resins.Through elementary analysis, nuclear-magnetism,
Infrared analysis confirms that molar content shared by vinyl chloride construction unit is 58.0% in vinyl chloride copolymer resin;Vinylidene chloride
Molar content shared by construction unit is 25.6%;Molar content shared by n-butyl acrylate construction unit is
10.9%;Molar content shared by maleic anhydride construction unit is 5.5%.
Polymer data:252 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.56g/cm3, porosity 42%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 58.7MPa, shock strength (GB/T1843-
1996) it is 35.2KJ/m2, specifically it is shown in Table 1.
Embodiment 5
Under the protection of inert gas, 6L high purity deionized waters, 2408g chlorine are added into 10L stainless steel autoclaves
Vinyl monomer, 12g sodium peroxydisulfates, 28g sodium acid carbonates, 125g hydroxypropyl methyl celluloses (hydroxypropyl content 6.3mol%) and
60g polyvinyl alcohol (alcoholysis degree 65%), pre-dispersed 25min is stirred at room temperature, heats up and anti-at 55 DEG C of controlling reaction temperature
30min is answered, then adds 296g vinylidene chloride monomers and 242g n-butyl acrylate monomers, after completing monomer addition, then is added
20min is reacted at 55 DEG C of 4g sodium peroxydisulfates and controlling reaction temperature, 60g maleic anhydride monomers are then added dropwise, heats up and controls
60 DEG C of reaction temperature processed, when polymerization pressure declines 0.2MPa, add 18g n-dodecyl mercaptans and stop stirring, drop
Low reaction temperatures, residual gas in releasing reactor discharge and filtered, washing and drying process, obtain 2635g vinyl chloride and be total to
Copolymer resin.Through shared by vinyl chloride construction unit in elementary analysis, nuclear-magnetism, infrared analysis confirmation vinyl chloride copolymer resin moles
Percentage composition is 77.9%;Molar content shared by vinylidene chloride construction unit is 11.0%;N-butyl acrylate structure list
Molar content shared by member is 8.9%;Molar content shared by maleic anhydride construction unit is 2.2%.
Polymer data:219 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.65g/cm3, porosity 47%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 66.1MPa, shock strength (GB/T1843-
1996) it is 32.4KJ/m2, specifically it is shown in Table 1.
Embodiment 6
Under the protection of inert gas, 6L high purity deionized waters, 2415g chlorine are added into 10L stainless steel autoclaves
Vinyl monomer, 12g sodium peroxydisulfates, 28g sodium acid carbonates, 95g hydroxypropyl methyl celluloses (hydroxypropyl content 6.3mol%) and
90g polyvinyl alcohol (alcoholysis degree 65%), pre-dispersed 25min is stirred at room temperature, heats up and anti-at 55 DEG C of controlling reaction temperature
30min is answered, then adds 296g vinylidene chloride monomers and 242g n-butyl acrylate monomers, after completing monomer addition, then is added
20min is reacted at 55 DEG C of 4g sodium peroxydisulfates and controlling reaction temperature, 60g maleic anhydride monomers are then added dropwise, heats up and controls
60 DEG C of reaction temperature processed, when polymerization pressure declines 0.2MPa, add 18g n-dodecyl mercaptans and stop stirring, drop
Low reaction temperatures, residual gas in releasing reactor discharge and filtered, washing and drying process, obtain 2642g vinyl chloride and be total to
Copolymer resin.Through shared by vinyl chloride construction unit in elementary analysis, nuclear-magnetism, infrared analysis confirmation vinyl chloride copolymer resin moles
Percentage composition is 78.0%;Molar content shared by vinylidene chloride construction unit is 10.8%;N-butyl acrylate structure list
Molar content shared by member is 9.0%;Molar content shared by maleic anhydride construction unit is 2.2%.
Polymer data:216 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.73g/cm3, porosity 44%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 66.8MPa, shock strength (GB/T1843-
1996) it is 34.5KJ/m2, specifically it is shown in Table 1.
Embodiment 7
Under the protection of inert gas, 6L high purity deionized waters, 2407g chlorine are added into 10L stainless steel autoclaves
Vinyl monomer, 12g sodium peroxydisulfates, 28g sodium acid carbonates, 60g hydroxypropyl methyl celluloses (hydroxypropyl content 6.3mol%) and
125g polyvinyl alcohol (alcoholysis degree 65%), pre-dispersed 25min is stirred at room temperature, heats up and anti-at 55 DEG C of controlling reaction temperature
30min is answered, then adds 296g vinylidene chloride monomers and 242g n-butyl acrylate monomers, after completing monomer addition, then is added
20min is reacted at 55 DEG C of 4g sodium peroxydisulfates and controlling reaction temperature, 60g maleic anhydride monomers are then added dropwise, heats up and controls
60 DEG C of reaction temperature processed, when polymerization pressure declines 0.2MPa, add 18g n-dodecyl mercaptans and stop stirring, drop
Low reaction temperatures, residual gas in releasing reactor discharge and filtered, washing and drying process, obtain 2624g vinyl chloride and be total to
Copolymer resin.Through shared by vinyl chloride construction unit in elementary analysis, nuclear-magnetism, infrared analysis confirmation vinyl chloride copolymer resin moles
Percentage composition is 77.8%;Molar content shared by vinylidene chloride construction unit is 11.0%;N-butyl acrylate structure list
Molar content shared by member is 9.1%;Molar content shared by maleic anhydride construction unit is 2.1%.
Polymer data:217 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.68g/cm3, porosity 46%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 65.9MPa, shock strength (GB/T1843-
1996) it is 31.0KJ/m2, specifically it is shown in Table 1.
Embodiment 8
Under the protection of inert gas, 6L high purity deionized waters, 2395g chlorine are added into 10L stainless steel autoclaves
(hydroxypropyl content is for vinyl monomer, 12g sodium peroxydisulfates, 28g ABVNs, 60g hydroxypropyl methyl celluloses
6.3mol%) and 125g polyvinyl alcohol (alcoholysis degree 65%), pre-dispersed 25min is stirred at room temperature, heats up and control reaction
30min is reacted at 55 DEG C of temperature, then adds 296g vinylidene chloride monomers and 241g acrylic acid-2-ethyl caproite monomers, is completed
After monomer addition, then add and react 20min at 55 DEG C of 4g ABVNs and controlling reaction temperature, 60g is then added dropwise along fourth
Enedioic acid anhydride monomer, heat up simultaneously 60 DEG C of controlling reaction temperature, when polymerization pressure declines 0.2MPa, adds 18g positive 12
Alkyl hydrosulfide simultaneously stops stirring, reduction reaction temperature, residual gas in releasing reactor, discharging and filtered, washing and drying
Processing, obtains 2648g vinyl chloride copolymer resins.Confirmed through elementary analysis, nuclear-magnetism, infrared analysis in vinyl chloride copolymer resin
Molar content shared by vinyl chloride construction unit is 78.1%;Molar content shared by vinylidene chloride construction unit is
10.9%;Molar content shared by n-butyl acrylate construction unit is 9.0%;Rubbed shared by maleic anhydride construction unit
Your percentage composition is 2.0%.
Polymer data:235 μm of the resin particle diameter of Coulter particle size analyzers measure;AutoPore-IV-9510 presses mercury
The resin apparent density of instrument measure is 0.75g/cm3, porosity 42%, specifically it is shown in Table 1.
Mechanical properties of polymer:Tensile strength (GB/T1040-2006) is 63.2MPa, shock strength (GB/T1843-
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
It was found from the data of table 1, the present invention on polyvinyl chloride main chain by introducing vinylidene chloride, unrighted acid and suitable
Anhydride maleique, and adjust whole, improvement dispersant dosage and match the vinyl chloride copolymer resin being prepared, grain form rule
It is whole, fine and close, there is relatively low porosity and compared with high apparent density, its fabricated product possesses excellent tensile property and impact resilience
Energy.