CN106046218A - Method for preparing uvioresistant polyvinyl chloride master batch - Google Patents
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- CN106046218A CN106046218A CN201610384348.4A CN201610384348A CN106046218A CN 106046218 A CN106046218 A CN 106046218A CN 201610384348 A CN201610384348 A CN 201610384348A CN 106046218 A CN106046218 A CN 106046218A
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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
- C08F2/20—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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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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Abstract
The invention discloses a method for preparing uvioresistant polyvinyl chloride master batch. The method includes the following steps that firstly, 100 parts of ionized water and 100 parts of nano-ceria sol are added into a stainless steel reaction kettle, and stirring is carried out for 10 min; secondly, 20 parts of a suspension colloid protection agent which is a water-soluble high-molecular compound and 1 part of a pH buffer agent are added into the reaction kettle in the stirring state, stirring continues for 60 min, and air in the kettle is displaced with nitrogen; thirdly, 40 parts of vinyl chloride monomers are added into the reaction kettle, and stirring is carried out for 60 min; fourthly, an initiator is added, the temperature is slowly increased to 60 DEG C in the stirring state, after a polymerization reaction is carried out for 3-4 h, 0.2 part of a polymerization terminator is added when the pressure in the reaction kettle is reduced to 0.10-0.15 MPa, the reaction is finished, depressurizing is carried out, discharging is carried out, slurry is subjected to centrifugal drying, and the ultraviolet-shielding ceria composite polyvinyl chloride master batch is obtained. Ceria particles prepared through in-situ polymerization are uniformly dispersed in a polyvinyl chloride matrix, the material is uniform in microstructure and capable of shielding ultraviolet completely, and the service life of the product can be prolonged.
Description
Technical field
The invention belongs to field of chemical engineering, be specifically related to a kind of method preparing uvioresistant chloride master batch.
Background technology
Inorganic nano material is generally divided into processing and is blended and two kinds of methods of in-situ polymerization the modification of plastics.The most poly-
Conjunction method is the best approach, and nano material can form nano level coexisting with polymer macromolecule, it is achieved has polymer
Effect modification.The nano inorganic material modification to polymer, or to property modification such as the mechanics of matrix polymer or right
Optics magnetics etc. are properties modifying.Polrvinyl chloride is common widely used engineering plastics, various modification technology occurs
And approach.Modified to the in-situ polymerization of polrvinyl chloride with nano-calcium carbonate, nano-calcium carbonate is as the filler of polrvinyl chloride, not only
Achieve the modified effect to polrvinyl chloride high intensity and high tenacity, and reduce production cost in process plastic processing.
But this modification can not realize the modification to vinyl chloride character.
Nano-cerium oxide absorbs and uv reflectance material as strong, has the strength function of shielding to ultraviolet, when it
It is dispersed in polrvinyl chloride with nano-particle, the performance of the strongest shielding ultraviolet rays of polrvinyl chloride base material will be given, for improving
The service life of polrvinyl chloride will produce actively impact.Meanwhile, nano-cerium oxide is as the nothing being well dispersed in polrvinyl chloride
Machine material, to improve polrvinyl chloride mechanical property also will produce good effect, it is possible to increase the tensile strength of polrvinyl chloride with
Toughness.Therefore, develop and use nano-cerium oxide polyvinyl chloride composite materials, there is positive effect.
Summary of the invention
Present invention aims to above-mentioned the deficiencies in the prior art, it is provided that a kind of polychlorostyrene second preparing anti-ultraviolet radiation
The method of alkene masterbatch, this masterbatch has high ultraviolet absorption ability and instead through can produce polychloroethylene blended with raw material
Penetrate the polrvinyl chloride product of ability.
The technical scheme is that and be achieved in that:
A kind of method preparing uvioresistant chloride master batch, concrete grammar step is as follows,
S1: in stainless steel cauldron, adds 100 parts of ionized waters, adds 100 parts of nano-cerium oxide colloidal sols, stirs 10min；
S2: under stirring, adds 20 portions of suspension colloid protective agents, for water-soluble high-molecular compound, 1 part to reactor
PH buffer agent, continues stirring 60min, with air in nitrogen displacement still；
S3: add 40 parts of Vinyl Chloride Monomer in reactor, stir 60min；
S4: add initiator, under stirring, be slowly warmed up to 60 DEG C, after polyreaction 3-4h, pressure in question response still
Being down to during 0.10-0.15MPa add 0.2 part of polymerization terminator, terminate reaction, blood pressure lowering, discharging, pulp centrifuged, drying is received
Rice cerium oxide composite polrvinyl chloride masterbatch.
The temperature of suspension polymerization of VC, this is the key factor controlling polrvinyl chloride molecular weight.Suspension polymerization of VC
Time, the molecular weight of polymer is closely related with the chain transfer constant of monomer, and the chain transfer constant of Vinyl Chloride Monomer is temperature
Function, during suspension polymerization of VC, the molecular weight of polymer is controlled by polymerization temperature.Therefore, it is precisely controlled polymerization temperature
It it is the key preparing polymer molecular weight.
The terminator of suspension polymerization of VC, its objective is that the free radical making the free end of the chain of polymerization inactivates, will not live
The coupling of property macromolecular chain, ensures the molecular weight narrow ditribution of polrvinyl chloride as far as possible.Interior pressure at polymeric kettle drops to
During below 0.1MPa, the polymerization conversion speed of Vinyl Chloride Monomer declines, in order to overcome the coupling reaction of possible active macromolecules,
Terminator must be added when reacting kettle inner pressure is at 0.1-0.15MPa.And the addition of terminator, Vinyl Chloride Monomer certainly will be caused
Trans-utilization rate decline, so implement suspension polymerization of VC time, the most a certain proportion of Vinyl Chloride Monomer is not polymerized.
This partial monosomy must recycle, and otherwise can cause wastage of material and environmental pollution.
In described step S1, nano-cerium oxide colloidal sol is the aqueous solution with sodium hexameta phosphate as dispersant, and dispersant is
About 0.5%.The colloid prepared with cerous nitrate Hydrolyze method, its solid content is 1～20%.
In described step S1, nano-cerium oxide colloidal sol is monodisperse status, and particle diameter is in 50-500nm, mean diameter 100nm.
In described step S1, nano-cerium oxide colloidal sol is to be added directly into polymerization system with the hydrosol of 5-20% cerium oxide
In.
In described step S2 suspension colloid protective agent be the polyvinyl alcohol of mass fraction 5% solution, polyvinylpyrrolidone,
Carboxymethyl cellulose, one or more in hydroxypropyl methyl cellulose ether, hydroxymethyl cellulose.
In described step S2, pH buffer agent is ammonium hydrogen carbonate, ammonium acetate, sodium carbonate, dibastic sodium phosphate or ammonia.
In described step S4, initiator is azodiisobutyronitrile, dibenzoyl peroxide, peroxy dicarbonate hexichol oxygen second
Base ester or double (2-ethyl) ester of peroxy dicarbonate.
In described step S4, terminator is hydroquinone, diethyl hydroxylamine, SDD, vulcanizes more
Sodium or sodium nitrite.
In described method step, to be followed successively by deionized water, nano-cerium oxide colloidal sol, polyvinyl alcohol molten for each component order of addition
Liquid, ammonium hydrogen carbonate, Vinyl Chloride Monomer, initiator.The reasonably charging technology of science, it is possible to ensure the height of ceria nanoparticles
Degree be dispersed in PVC base system, this be polyvinyl chloride composite materials realize shielding ultraviolet rays function key link it
One.
In-situ polymerization technology is in the case of nano-particle is present in vinyl chloride monomer polymerization reactions system, and absorption is being received
Vinyl Chloride Monomer on rice grain surface, polymerization defines the compound of the macromolecules adsorption nucleocapsid structure on cerium oxide particle surface
Thing.Nano-particle also exists intimate contact and affinity with being polymerized monomer, and Vinyl Chloride Monomer is causing in polymerization process, nano oxygen
Change the infiltration of cerium single dispersing ground between polrvinyl chloride macromolecular chain, promote nano-particle single dispersing in PVC base system.In situ
Polymerization technique can efficiently solve nano-particle dispersion problem in PVC base system.Meanwhile, nano grain surface
Active group can also there is certain chemistry and physical action with Vinyl Chloride Monomer or polrvinyl chloride long-chain, effectively increase
Strong inorganic matter and organic interaction force, performance and character to material can bring the biggest improvement.Nano-cerium oxide is made
Absorb and uv reflectance material for strong, there is the strength function of shielding to ultraviolet, when it is dispersed in polychlorostyrene with nano-particle
In ethylene, the performance of the strongest shielding ultraviolet rays of polrvinyl chloride base material will be given, for improving the use longevity of polrvinyl chloride product
Life will produce actively impact.Meanwhile, nano-cerium oxide is as the inorganic material being well dispersed in polrvinyl chloride, to improving polychlorostyrene
The mechanical property of ethylene also will produce good effect, it is possible to increase the tensile strength of polrvinyl chloride and toughness.Therefore, develop and make
Use nano-cerium oxide polyvinyl chloride composite materials, there is positive effect.
The present invention uses said method to have the advantages that
1. the obtained nano-cerium oxide complex of suspension polymerization of VC, be a kind of cerium oxide be that core polrvinyl chloride is
The nucleocapsid structure of shell, cerium oxide is the nucleator of chloroethylene polymerization, forms chloroethylene polymerization colloidal solid, along with gathering of vinyl chloride
Closing, colloidal solid is transformed into the polymer beads of kernel coating cerium oxide particle.In the course of the polymerization process, chloroethylene polymerization colloid
Grain, it may occur that reunion coalescence, so the polyvinyl chloride particles formed is bulky grain, is to be cerium oxide by many kernels
The many little granule composition of grain, but cerium oxide is distributed in PVC base system with remaining single dispersing.This structure, both
Ensure that the mechanics potentiation to polrvinyl chloride, in turn ensure that nano-scale particle, to the absorption of ultraviolet and reflection, reaches
Arrive the pvc material purpose shielded completely to ultraviolet, ensure the service life of polrvinyl chloride simultaneously.
2. the cerium oxide polyvinyl chloride composite materials of nucleocapsid structure, its cerium oxide solid content is higher, and up to 50% more than, make
The masterbatch being processed further for polrvinyl chloride, in the blended processing in later stage, the further dispersing cerium oxide granule of meeting, rolling into a ball
Poly-cerium oxide particle disperses further, it is ensured that cerium oxide particle is dispersed in PVC base system, the microcosmic knot of material
Structure is uniform, and the embodiment of guarantee polrvinyl chloride base material macro property reaches the purpose of the complete shielding properties of ultraviolet.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but be not intended that the present invention any
Limit.
Embodiment 1
A kind of method preparing uvioresistant chloride master batch, concrete grammar step is as follows,
S1: in stainless steel cauldron, adds 100 parts of ionized waters, adds 100 parts of nano-cerium oxide colloidal sols, stirs 10min；
S2: under stirring, adds 20 portions of suspension colloid protective agents, for water-soluble high-molecular compound, 1 part to reactor
PH buffer agent, continues stirring 60min, with air in nitrogen displacement still；
S3: add 40 parts of Vinyl Chloride Monomer in reactor, stir 60min；
S4: add initiator, under stirring, be slowly warmed up to 60 DEG C, after polyreaction 3-4h, pressure in question response still
Being down to during 0.14MPa add 0.2 part of polymerization terminator, terminate reaction, blood pressure lowering, discharging, pulp centrifuged, drying obtains nano oxidized
Cerium composite polrvinyl chloride masterbatch.
In described step S1, nano-cerium oxide colloidal sol is the aqueous solution with sodium hexameta phosphate as dispersant, and dispersant is
About 0.5%.The colloid prepared with cerous nitrate Hydrolyze method, its solid content is 15%.
In described step S1, nano-cerium oxide colloidal sol is monodisperse status, and particle diameter is in 50nm, mean diameter 100nm.
In described step S1, nano-cerium oxide colloidal sol is to be added directly in polymerization system with the hydrosol of 5% cerium oxide.
In described step S2, suspension colloid protective agent is the polyvinyl alcohol of mass fraction 5% solution.
In described step S2, pH buffer agent is ammonium hydrogen carbonate.
In described step S4, initiator is double (2-ethyl) ester of peroxy dicarbonate.
In described step S4, terminator is sodium nitrite.
In described method step, to be followed successively by deionized water, nano-cerium oxide colloidal sol, polyvinyl alcohol molten for each component order of addition
Liquid, ammonium hydrogen carbonate, Vinyl Chloride Monomer, initiator.
Embodiment 2
Method step is with embodiment 1, different technological parameters:
In 50L stainless steel cauldron, add deionized water 10kg, open stirring, add receiving of 10kg solid content 10%
Rice cerium oxide sol, stirs 10min；Open stirring, add 2kg polyvinylpyrrolidone 5% solution and protect as suspension colloid
Agent, 0.1kg ammonium hydrogen carbonate, as pH buffer agent, stirs 60min, with air in nitrogen or argon displacement still；It is filled with 4kg chloroethene
Alkene monomer, stirs 60min；Addition 40g azodiisobutyronitrile, as initiator, under stirring, is slowly warmed up to 60 DEG C of beginnings
Polymerization, after polyreaction 4h, in still, pressure is down to add the hydroquinone polymerization of 20g during 0.1MPa as terminator, end
Reaction, blood pressure lowering, discharging, pulp centrifuged drying obtains the polrvinyl chloride composite master batch of uvioresistant cerium-oxide contents about 20%.
Nano-cerium oxide colloidal sol is monodisperse status, and particle diameter is in 500nm, mean diameter 100nm.
Embodiment 3
Method step is with embodiment 1, different technological parameters:
In 50L stainless steel cauldron, add deionized water 10kg, open stirring, add receiving of 10kg solid content 20%
Rice cerium oxide sol, stirs 10min；Open stirring, add 2kg carboxymethyl cellulose 5% solution as suspension colloid protective agent,
0.1kg ammonium hydrogen carbonate, as pH buffer agent, stirs 60min, with air in nitrogen or argon displacement still；It is filled with 4kg vinyl chloride
Monomer, stirs 60min；Addition 40g peroxy dicarbonate hexichol oxygen ethyl ester, as initiator, under stirring, slowly heats up
Starting polymerization to 60 DEG C, after polyreaction 3.5h, in still, pressure is down to during 0.15MPa add the Methyl disulfide of 20g for ammonia
The polymerization of base sodium formate, as terminator, terminates reaction, and blood pressure lowering, discharging, it is many that pulp centrifuged drying obtains uvioresistant cerium-oxide contents
In the polrvinyl chloride composite master batch of 50%.
Nano-cerium oxide colloidal sol is monodisperse status, and particle diameter is in 100nm, mean diameter 100nm.
Embodiment 4
Method step is with embodiment 1, different technological parameters:
In 50L stainless steel cauldron, add deionized water 10kg, open stirring, add the nanometer of 10kg solid content 5%
Cerium oxide sol, stirs 10min；Open stirring, add 2kg hydroxypropyl methyl cellulose ether 5% solution and protect as suspension colloid
Protecting agent, 0.1kg ammonium hydrogen carbonate, as pH buffer agent, stirs 60min, with air in nitrogen or argon displacement still；It is filled with 4kg chlorine
Vinyl monomer, stirs 60min；Addition 40g dibenzoyl peroxide, as initiator, under stirring, is slowly warmed up to 60 DEG C
Starting polymerization, after polyreaction 3h, in still, pressure is down to add the diethyl hydroxylamine polymerization of 20g during 0.1MPa as terminating
Agent, terminates reaction, blood pressure lowering, discharging, and the polrvinyl chloride that pulp centrifuged drying obtains uvioresistant cerium-oxide contents about about 15% is multiple
Combination master batch.
Nano-cerium oxide colloidal sol is monodisperse status, and particle diameter is in 300nm, mean diameter 100nm.
Claims (9)
1. the method preparing uvioresistant chloride master batch, it is characterised in that: concrete grammar step is as follows,
S1: in stainless steel cauldron, adds 100 parts of ionized waters, adds 100 parts of nano-cerium oxide colloidal sols, stirs 10min；
S2: under stirring, adds 20 portions of suspension colloid protective agents to reactor, and for water-soluble high-molecular compound, 1 part of pH delays
Electuary, continues stirring 60min, with air in nitrogen displacement still；
S3: add 40 parts of Vinyl Chloride Monomer in reactor, stir 60min；
S4: adding initiator, under stirring, be slowly warmed up to 60 DEG C, after polyreaction 3-4h, in question response still, pressure is down to
Adding 0.2 part of polymerization terminator during 0.10-0.15MPa, terminate reaction, blood pressure lowering, discharging, pulp centrifuged drying obtains shielding ultraviolet
Line cerium oxide composite polrvinyl chloride masterbatch.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described step S1
Middle nano-cerium oxide colloidal sol is the aqueous solution with sodium hexameta phosphate as dispersant, the colloid prepared with cerous nitrate Hydrolyze method, and it is solid
Content is 1～20%.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described step S1
Middle nano-cerium oxide colloidal sol is monodisperse status, and particle diameter is in 50-500nm, mean diameter 100nm.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described step S1
Middle nano-cerium oxide colloidal sol is to be added directly in polymerization system with the hydrosol of 5-20% cerium oxide.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described step S2
Middle suspension colloid protective agent is the poly-vinyl alcohol solution of mass fraction 5%, the polyvinylpyrrolidone of mass fraction 5%, carboxylic first
Base cellulose, the one in hydroxypropyl methyl cellulose ether, hydroxymethyl cellulose.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described step S2
Middle pH buffer agent is ammonium hydrogen carbonate, ammonium acetate, sodium carbonate, dibastic sodium phosphate or ammonia.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described step S4
Middle initiator is azodiisobutyronitrile, dibenzoyl peroxide, peroxy dicarbonate hexichol oxygen ethyl ester or peroxy dicarbonate
Double (2-ethyl) ester.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described step S4
Middle terminator is hydroquinone, diethyl hydroxylamine, SDD, sodium polysulphide or sodium nitrite.
The method of preparation uvioresistant chloride master batch the most according to claim 1, it is characterised in that: described method walks
In Zhou each component order of addition be followed successively by deionized water, cerium oxide sol, poly-vinyl alcohol solution, ammonium hydrogen carbonate, Vinyl Chloride Monomer,
Initiator.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503730A (en) * | 2018-03-28 | 2018-09-07 | 鄂尔多斯市瀚博科技有限公司 | A kind of hot suspension polymerisation terminator of polyvinyl chloride and its application |
| CN109248638A (en) * | 2018-08-27 | 2019-01-22 | 华南理工大学 | A kind of nuclear case structure hybridization material and the preparation method and application thereof with anti-ultraviolet property |
| CN115197507A (en) * | 2022-06-10 | 2022-10-18 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of polyvinyl chloride ultraviolet shielding additive |
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| CN102675502A (en) * | 2012-05-18 | 2012-09-19 | 东华大学 | Production method of uvioresistant functional polrvinyl chloride |
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| CN102675502A (en) * | 2012-05-18 | 2012-09-19 | 东华大学 | Production method of uvioresistant functional polrvinyl chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503730A (en) * | 2018-03-28 | 2018-09-07 | 鄂尔多斯市瀚博科技有限公司 | A kind of hot suspension polymerisation terminator of polyvinyl chloride and its application |
| CN108503730B (en) * | 2018-03-28 | 2020-06-12 | 鄂尔多斯市瀚博科技有限公司 | Polyvinyl chloride thermal suspension polymerization terminator and application thereof |
| CN109248638A (en) * | 2018-08-27 | 2019-01-22 | 华南理工大学 | A kind of nuclear case structure hybridization material and the preparation method and application thereof with anti-ultraviolet property |
| CN109248638B (en) * | 2018-08-27 | 2021-06-08 | 华南理工大学 | Core-shell structure hybrid material with ultraviolet resistance and preparation method and application thereof |
| CN115197507A (en) * | 2022-06-10 | 2022-10-18 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of polyvinyl chloride ultraviolet shielding additive |
| CN115197507B (en) * | 2022-06-10 | 2023-11-14 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method and application of polyvinyl chloride ultraviolet shielding additive |
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