CN108586969A - A kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin - Google Patents
A kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin Download PDFInfo
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- CN108586969A CN108586969A CN201711431813.6A CN201711431813A CN108586969A CN 108586969 A CN108586969 A CN 108586969A CN 201711431813 A CN201711431813 A CN 201711431813A CN 108586969 A CN108586969 A CN 108586969A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of 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
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The present invention relates to a kind of suspension polymerizations of polyvinyl chloride/nano calcium carbonate compound resin, specifically prepare a kind of evenly dispersed and stable system modified nano calcium carbonate lotion, improve its interaction with polymeric matrix, then again with specific feed way, finally the obtained nano-calcium carbonate of suspension polymerisation disperses uniform polychloroethylene compound resin in water.Invention enhances the interaction with polymeric matrix, dispersion and filling in a polymer matrix is improved；It is slowly added into nano-calcium carbonate lotion in certain polymerization time section, solve agglomeration when nano-calcium carbonate is added together, it is allowed to be better dispersed in PVC base system and vinyl chloride, the tensile strength of the polychloroethylene compound resin of gained, impact strength is enhanced about more than once.
Description
Technical field
The invention belongs to chemical materials preparation fields, more particularly, to a kind of polyvinyl chloride/nano calcium carbonate compound resin
Suspension polymerization.
Background technology
Polyvinyl chloride is current common one of general-purpose plastics, is had extensively in fields such as construction material, tubing, packaging films
Application.In order to improve the toughness of pvc material, promote its application range, modified Nano is added into PVC base system
It is current main PVC modified means that calcium carbonate, which prepares polyvinyl-chloride/calcium carbonate composite material,.
Traditional melt blended method cannot so that calcium carbonate nano particle is evenly dispersed, the method for solution blending by
Solvent separates and recovers the restriction for the shortcomings of organic solvent pollution that is of high cost, introducing is big, is unfavorable for polyvinyl-chloride/calcium carbonate height
The popularization of performance compound resin produces；On the other hand, calcium carbonate surface contains the hydroxyl of a large amount of hydrophilic and oleophobics, is unfavorable for and polychlorostyrene
Ethylene forms strong interaction, causes after nano-calcium carbonate is added, the mechanical property of composite material is deteriorated instead.It is standby in recent years
It is concerned, pass through and vinyl chloride monomer be added in calcium carbonate suspension/dispersion and dispersant realizes in-situ suspension polymerization production
The method of polyvinyl chloride/nano calcium carbonate compound resin is added influence by calcium carbonate, vinyl chloride monomer, equally cannot by several times
Realize that nano-calcium carbonate is evenly dispersed in PVC base system.
Chinese patent CN1631920A discloses a kind of vinyl chloride/nano calcium carbonate in-situ polymerization resin preparation method.It should
Nano-calcium carbonate filler is uniformly dispersed by method in advance during preparing Corvic using suspension polymerization
In vinyl chloride monomer, make the surface of Nano filling particle that chemical reaction and physical absorption occur with vinyl chloride monomer, to carry
High polrvinyl chloride product physical mechanical property.The method, since stirring is happened in polymeric kettle, polymeric kettle stirring intensity cannot make
Nano-calcium carbonate is evenly dispersed.
Chinese patent CN1392177A discloses a kind of preparation method that nano modified chemical building material is polyvinyl chloride resin dedicated,
Its process is：Deionized water, nano-calcium carbonate, carbonic ester, hexadecanol, polyoxyethylene ether, hydroxypropyl methyl cellulose are carried out
Nano-calcium carbonate emulsification slurries are made in ultrasonic wave and microemulsified processing；Again by soft water, EHP, hydroxypropyl methyl cellulose, nanometer
Polymeric kettle is added in calcium carbonate slurry, and vinyl chloride monomer, cold stirring, the techniques such as heating polymerization and dry, packaging are added after vacuum.
For the technique due to the process of charging, nano-calcium carbonate agglomeration traits influence nano-calcium carbonate in polyvinyl chloride still than more prominent
Dispersion in resin.
Invention content
The present invention provides a kind of suspension polymerizations of polyvinyl chloride/nano calcium carbonate compound resin, are received for improving
Rice corpuscles interacts with polymeric matrix, realizes evenly dispersed high-performance polyvinyl chloride/nano calcium carbonate compound resin system
Standby technique.
To solve to reach above-mentioned purpose, using following measures：Prepare a kind of evenly dispersed and stable system modified Nano
Calcium carbonate emulsion improves its interaction with polymeric matrix, is then finally suspended in water with specific feed way again
Polymerization is made nano-calcium carbonate and disperses uniform polychloroethylene compound resin.
Specifically comprise the following steps：
A, the preparation of nano-calcium carbonate lotion：
1）Dispersant is added in water and is configured to the solution that mass concentration is 0.1-3%；
2）The step 1 under stirring）The middle calcium hydroxide that 7-14% is added, nucleus form accelerating agent, steric hindrance conditioning agent；
3）Under certain initial temperature, step 2）In be passed through high-purity carbon dioxide carry out carburizing reagent, when this system PH is dropped to
It stops the supple of gas or steam when neutral；
4）By step 3）Obtained calcium carbonate suspension is warming up to 60-90 DEG C, stirring while modifier solution is added is modified,
Time is 0.5-2.5 hour, uses pH adjusting agent to adjust the pH value of modified calcium carbonate suspension as 8-9, is disperseed
Uniform and stable system nano-calcium carbonate lotion.
Dispersant as described above uses dispersant used in suspension polymerization, such as cellulose family, poly- second
Enol class etc., does not interfere with suspension polymerization thus.
It is a kind of in EDTA, EDETATE SODIUM salt, sodium citrate, glucose, sodium sulphate that nucleus as described above, which forms accelerating agent,
Or more than one.
Steric hindrance conditioning agent as described above is magnesium chloride, neopelex, lauryl sodium sulfate, three second
It is one or more kinds of in hydramine, magnesium sulfate.
Certain initial temperature as described above is 5-35 DEG C.
High-purity carbon dioxide a concentration of 70% or more as described above, due to the use of high-purity carbon dioxide be carbonized it is anti-
It answers, it is necessary to control certain ventilatory capacity and use jacket water (J.W.) controlling reaction temperature, the carburizing temperature of system is made to control opposite
In relatively narrow range, the calcium carbonate particle diameter distribution of generation is uniform；In 0.5-2 L/min, chuck coolant-temperature gage is 5- for ventilatory capacity control
30℃。
Stirring as described above can be also carried out at the same time with ultrasonic wave, ultrasonic power 100-1500W, frequency 10-
50KHz。
Modifying agent as described above is one or more kinds of in phthalate, aliphatic acid and its esters, coupling agent.
Nano-calcium carbonate lotion average grain diameter as described above is between 60-100nm.
Its solid content of nano-calcium carbonate lotion as described above is the 3-10% of monomer mass.
B, nano-calcium carbonate lotion and the compound process for suspension polymerization of vinyl chloride：
The reagent and additive in polymerization such as a certain amount of water, dispersant, initiator, PH conditioning agents are added in polymeric kettle, it is added after removing air
It is cold after vinyl chloride monomer to stir 30 minutes, be warming up to certain polymerization temperature and carry out polymerisation, when polymerization after a certain period of time, namely
After polymerisation 10-240 minutes, the nano-calcium carbonate lotion in above-mentioned steps a is added, as the pressure reduction 0.1- of polymeric kettle
It after 0.3 MPa, discharges after terminator is added, is polyvinyl chloride/nano calcium carbonate by the product after stripping, centrifugation, drying
Compound resin.
Dispersant when polymerization as described above is a kind of or a kind of in hydroxypropyl emthylcellulose or polyvinyl alcohol
More than, such as HPMC, KH-20, TCR-7524.
PH conditioning agents as described above include a kind of in sodium bicarbonate, ammonium hydrogen carbonate or ammonium hydroxide, and polymerization system PH is adjusted
Value, can also improve particulate resin form and resin apparent density etc..
As described above removal polymeric kettle in air manner vacuumize with nitrogen displacement etc..
Polymerization temperature as described above is 45-70 DEG C.
Polymerization certain time as described above refers in polymerisation 10-240 minutes；The moment is added as polymerization in nano-calcium carbonate
Some time point in reaction 10-240 minutes, and be slowly added dropwise into polymeric kettle using feed pump and participate in reaction, nanometer is added
The flow control of calcium carbonate emulsion in 20-120mL/min, nano-calcium carbonate lotion be added the time required to polymeric kettle control for
10-60 minutes.
The principle of the invention is：Polyvinyl chloride does not dissolve in polyvinyl monomer, and polymerization initial stage polyvinyl chloride chain free radical increases
To certain length（The degree of polymerization is 10-30）Afterwards, precipitation tendency, under very low conversion ratio, about 50 free radical balls of string are just had
Winding coalesces together, and is precipitated out to form primary particle.Primary particle cannot be individually nucleated and extremely unstable, it is easy to again
Flocculation about carries out second by 1000 primary particles and flocculates, is coalesced as primary particle core.Primary particle core is grown into just again
Grade particle, primary particle flocculation aggregation and primary particle continue to grow up, and here it is the granulation process of polyvinyl chloride.Polymerization
It is mainly carried out in polyvinyl chloride/vinyl chloride swelling body, does not re-form new first core, primary particle number is not also further added by, at this time
First core or primary particle are dispersed stably in drop, uniformly growing up slowly.
Evenly dispersed nano-calcium carbonate lotion is slowly added dropwise during polymerization as described above, is conducive to nano-sized carbon
Sour calcium is dispersed in primary particle or primary particle core or primary particle, or is intertwined with these particles, finally in grain
Son is grown up the process of coalescence, and Nano particles of calcium carbonate will be uniformly dispersed in PVC base system.This feed postition solution
It has determined the agglomeration traits generated when nano-calcium carbonate early period is added together.
The present invention is prepared for a kind of evenly dispersed and stable system modified nano calcium carbonate lotion, enhances and polymer
The interaction of matrix improves dispersion and filling in a polymer matrix；It is slowly added into certain polymerization time section
Nano-calcium carbonate lotion solves agglomeration when nano-calcium carbonate is added together, is allowed to be better dispersed in polyvinyl chloride-based
In body and vinyl chloride, the tensile strength of the polychloroethylene compound resin of gained, impact strength is enhanced about more than once.
Specific implementation mode
Embodiment 1：
A, a kind of evenly dispersed and stable system modified nano calcium carbonate lotion is prepared：
1）Be added in the 2L glass kettles containing 1200 mL water dispersant 12g HPMC be configured to mass concentration be 1% it is molten
Liquid；
2）120g calcium hydroxides, the EDETATE SODIUM of 2.4g, 2.4g lauryl sodium sulfate, 3.6g chlorine are added under stirring
Change magnesium；
3）Under 10 DEG C of initial temperature, it is passed through high-purity carbon dioxide and carries out carburizing reagent, ventilatory capacity 1L/min, as system PH
When dropping to neutrality, stop the supple of gas or steam；
4）Calcium carbonate suspension is warming up to 85 DEG C, in the case where ultrasonic wave and stirring exist simultaneously, it is molten that odium stearate is added
Liquid is modified, and the time is 1 hour, and then regulation system PH is 8-9, is thus uniformly dispersed and stable system
Nano-calcium carbonate lotion.
B, nano-calcium carbonate lotion and the compound process for suspension polymerization of vinyl chloride：
Put into 12.8kg water into 20 L polymeric kettles, the 7507P of 2.75 g, 1.1 g KH-20 polyvinyl alcohol dispersants
Aqueous solution, active EPH composite initiators in the Tx99 and 3.4 g of 0.95 g high activities, the PH conditioning agent ammonium hydrogen carbonate of 4 g,
4kg vinyl chloride monomer is added in 3 g liquid zinc etc. after vacuumizing, open stirring to 5 r/s, cold to stir 30 min, it is cold stirred after 30
It is warming up to 57.5 ± 0.5 DEG C of reactions in min, after reacting 50min, nano-calcium carbonate breast in step a is slowly added to by feed pump
Liquid, control were added at 30 minutes or so, then steadily controlled polymerisation, and terminator is added after 0.1 MPa of pressure reduction and goes out
Material obtains product after stripping, drying and packaging process.
C, processing formula：100 parts of polyvinyl chloride；5 parts of lead salt stabilizer；10 parts of CPE；0.1 part of PE waxes；Precipitated calcium carbonate
10 parts；1 part of odium stearate.Resin 1 and the present embodiment compound resin is taken to test its mechanical property by identical processing formula, data are such as
Following table.
Embodiment 2：
A, a kind of evenly dispersed and stable system modified nano calcium carbonate lotion is prepared：
1）The HPMC that dispersant 12g is added in the 2L glass kettles containing 1200mL water is configured to the solution that mass concentration is 1%；
2）120g calcium hydroxides, the EDETATE SODIUM of 2.4g, 2.4g lauryl sodium sulfate, 3.6g chlorinations are added under stirring
Magnesium；
3）Under 10 DEG C of initial temperature, it is passed through high-purity carbon dioxide and carries out carburizing reagent, ventilatory capacity 1L/min, as system PH
When dropping to neutrality, stop the supple of gas or steam；
4）Calcium carbonate suspension is warming up to 85 DEG C, in the case where ultrasonic wave and stirring exist simultaneously, it is molten that odium stearate is added
Liquid is modified, and the time is 1 hour, and then regulation system PH is 8-9, is thus uniformly dispersed and stable system
Nano-calcium carbonate lotion；
B, nano-calcium carbonate lotion and the compound process for suspension polymerization of vinyl chloride：
12.8kg water is put into 20 L polymeric kettles after nitrogen displacement, the 7507P of 2.75 g, the KH-20 of 1.1 g are PVA mixed
The aqueous solution for closing dispersant, active EPH composite initiators in the Tx99 and 3.4 g of 0.95 g high activities, 4 g PH conditioning agents
4kg vinyl chloride monomer is added in ammonium hydrogen carbonate, 3 g liquid zinc etc., opens stirring to 5 r/s, cold to stir 30 min, it is cold stirred after 30
It is warming up to 57.5 ± 0.5 DEG C of reactions in min, after reacting 120min, nano-calcium carbonate in step a is slowly added to by feed pump
Lotion, control were added at 30 minutes or so, then steadily control polymerisation, terminator is added after 0.1 MPa of pressure reduction
Discharging obtains product after stripping, drying and packaging process.
C, processing formula：100 parts of polyvinyl chloride；5 parts of lead salt stabilizer；10 parts of CPE；0.1 part of PE waxes；Precipitated calcium carbonate
10 parts；1 part of odium stearate.Resin 1 and the present embodiment compound resin is taken to test its mechanical property by identical processing formula, data are such as
Following table.
| Tensile strength/（MPa） | Impact strength/（KJ/㎡） | |
| Resin 1（Blank resin） | 42.2 | 14.6 |
| 2 compound resin of embodiment | 44.6 | 30.4 |
Implement 3：
Embodiment 3 with Examples 1 and 2 the difference is that in water be added dispersant be configured to mass concentration be 0.1% it is molten
Liquid；7% calcium hydroxide is added under stirring；The high-purity carbon dioxide a concentration of 70% being passed through；After polymerisation 10min,
Terminator is added after polymerization pressure reduces 0.1MPa.
Implement 4：
Embodiment 4 and embodiment 1-3 is configured to the solution that mass concentration is 3% the difference is that dispersant is added in water；
14% calcium hydroxide is added under stirring；The high-purity carbon dioxide a concentration of 100% being passed through；After polymerisation 240min,
Terminator is added after polymerization pressure reduces 0.3MPa.
Claims (8)
1. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin, includes the following steps：
A, the preparation of nano-calcium carbonate lotion：
1）Dispersant is added in water and is configured to the solution that mass concentration is 0.1-3%；
2）The step 1 under stirring）The middle calcium hydroxide that 7-14% is added, nucleus form accelerating agent, steric hindrance conditioning agent；
3）Under certain initial temperature, step 2）In be passed through high-purity carbon dioxide carry out carburizing reagent, when this system PH is dropped to
It stops the supple of gas or steam when neutral；
4）By step 3）Obtained calcium carbonate suspension is warming up to 60-90 DEG C, stirring while modifier solution is added is modified,
Time is 0.5-2.5 hours, and pH adjusting agent is used to adjust the pH value of modified calcium carbonate suspension as 8-9, and it is equal to obtain dispersion
Even and stable system nano-calcium carbonate lotion；
B, nano-calcium carbonate lotion and the compound suspension polymerisation of vinyl chloride：
The reagent and additive in polymerization such as a certain amount of water, dispersant, initiator, pH adjusting agent are added in polymeric kettle, are added after removing air
It is cold after vinyl chloride monomer to stir 30 minutes, it is warming up to polymerization temperature and carries out polymerisation, when polymerizeing after a certain period of time, above-mentioned step is added
Nano-calcium carbonate lotion in rapid a discharges after terminator is added after polymeric kettle pressure reduction 0.1-0.3 MPa, passes through vapour
Carry, centrifuge, dry after product be polyvinyl chloride/nano calcium carbonate compound resin.
2. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin as described in claim 1, feature exist
In dispersant be the one or more in hydroxypropyl emthylcellulose or polyvinyl alcohol.
3. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin as described in claim 1, feature exist
In above-mentioned steps a 3）In certain initial temperature be 5-35 DEG C.
4. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin as described in claim 1, feature exist
In a concentration of 70-100% of high-purity carbon dioxide.
5. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin as described in claim 1, feature exist
Refer in polymerisation 10-240 minutes in polymerization certain time.
6. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin as described in claim 1, feature exist
It is one or more in EDTA, EDETATE SODIUM salt, sodium citrate, glucose, sodium sulphate to form accelerating agent in above-mentioned nucleus.
7. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin as described in claim 1, feature exist
In above-mentioned steric hindrance conditioning agent be magnesium chloride, neopelex, lauryl sodium sulfate, triethanolamine, magnesium sulfate
Middle one or more.
8. a kind of suspension polymerization of polyvinyl chloride/nano calcium carbonate compound resin as described in claim 1, feature exist
In be added nano-calcium carbonate lotion flow control in 20-120mL/min.
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| CN109319815A (en) * | 2018-10-31 | 2019-02-12 | 吴亚良 | A kind of preparation method of nanometer calcium carbonate |
| CN109319815B (en) * | 2018-10-31 | 2020-11-20 | 绍兴市慧融臻合新能源科技有限公司 | Preparation method of nano calcium carbonate |
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