CN106589972A - Antibacterial hydrotalcite grafting-modified polyvinyl chloride composite pipe material and preparation method thereof - Google Patents
Antibacterial hydrotalcite grafting-modified polyvinyl chloride composite pipe material and preparation method thereof Download PDFInfo
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- CN106589972A CN106589972A CN201611007847.8A CN201611007847A CN106589972A CN 106589972 A CN106589972 A CN 106589972A CN 201611007847 A CN201611007847 A CN 201611007847A CN 106589972 A CN106589972 A CN 106589972A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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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
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses an antibacterial hydrotalcite grafting-modified polyvinyl chloride composite pipe material, which is composed of, by weight, 70-90 parts of polyvinyl chloride, 6-12 parts of glycidyl methacrylate, 2-5 parts of SiO2, a proper amount of acetone and a proper amount of methanol, 10-16 parts of hydrotalcite, 40-60 parts of dimethyl sulfoxide, 0.3-1 part of stannic chloride, 1-2 parts of an organic tin thermal-stabilizer, 5-9 parts of chlorinated polyethylene, 1-3 parts of oxidized polyethylene wax, 2-4 parts of dioctyl phthalate, 3-5 parts of ferric nitrate, 6-12 parts of nano titanium dioxide, a proper amount of deionized water, and 1-4 parts of zinc oxide. In the invention, the polyvinyl chloride and the glycidyl methacrylate are subjected to in-situ grafting to prepare a grafted product PVC-cg-GMA, and then through a grafting reaction between epoxy groups in the glycidyl methacrylate and hydrotalcite, the polyvinyl chloride pipe material is improved in thermal stability and weather resistance and also has excellent mechanical performance.
Description
Technical field
The present invention relates to the technology of preparing of polychloroethylene pipes, and in particular to a kind of antimicrobial form brucite graft modification polychlorostyrene
Ethylene composite pipe and preparation method thereof.
Background technology
Polychloroethylene pipes occupy an important position in numerous plastic pipes, and which has light weight, acid-alkali-corrosive-resisting, defeated
When sending fluid, resistance is little, insulating properties is excellent, construction is rapid easily, long service life, secondary operations are convenient, raw material sources fill
The advantages of foot, low price, it is widely used in the fields such as work, agricultural production and daily life.However, polrvinyl chloride itself
Existing defects and deficiency, such as heat stability are poor, and plasticization is unstable, volatile migration, boardy product be in fragility, shock resistance
Difference etc..
Meng Li, Zhao Jiruo et al. are at which《Situ-formed graft prepares PVC semi-interpenetrating network polymers and its sign is ground with performance
Study carefully》In-situ chlorinated graft method method is adopted in one text by PVC and glycidyl methacrylate (GMA) graft-blending, Zhi Houli
Crosslink poly (glycidyl methacrylate) to form cross-linked network and mutually pass through with PVC linear macromolecule chains with hexamethylene diamine
Wear, prepare the semi-interpenetrating network polymer with PVC as substrate, improve dynamic mechanical and heat stability of PVC etc..
Brucite can decompose generation HCl with polrvinyl chloride and react, and can play heat stabilization to polrvinyl chloride,
And brucite and some other thermally-stabilised auxiliary agent compound tense, heat stabilization becomes apparent from；In the absorbable sunlight of brucite
Ultraviolet, and be translated into heat and discharge, reduce polrvinyl chloride and be subject to the direct irradiation of intense UV rays and degrade
Probability, improves weatherability；Brucite contains and combines water, and has veneer structure, can absorb what polrvinyl chloride burning was released
Heat, suppresses the generation of smog, improves anti-flammability；Therefore, brucite be a kind of excellent, multi-functional polrvinyl chloride auxiliary agent or
Modifying agent.
Therefore the present invention prepares graft product PVC- using polrvinyl chloride and glycidyl methacrylate situ-formed graft
Cg-GMA, afterwards using the epoxide group and brucite graft reaction of glycidyl methacrylate, improves polrvinyl chloride
The heat stability of tubing, weather resistance, while with excellent mechanical property.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of antimicrobial form brucite graft modification polyvinyl chloride composite pipe
And preparation method thereof.
A kind of antimicrobial form brucite graft modification polyvinyl chloride composite pipe, is made up of the raw material of following weight portion：Polychlorostyrene
Ethylene 70-90 parts, glycidyl methacrylate 6-12 part, SiO2 2-5 parts, acetone in proper, appropriate methanol, brucite 10-
16 parts, dimethyl sulfoxide 40-60 parts, butter of tin 0.3-1 parts, organo-tin het stabilizer 1-2 parts, chlorinated polyethylene 5-9 parts, oxygen
Change Tissuemat E 1-3 parts, dioctyl phthalate 2-4 parts, ferric nitrate 3-5 parts, nano titanium oxide 6-12 parts, deionized water
In right amount, Zinc Oxide 1-4 part.
Comprise the following steps that：
（1）Polyvinyl chloride graft glycidyl methacrylate（PVC-cg-GMA）Preparation：
Pre-dried polrvinyl chloride is added in the there-necked flask equipped with agitator, thermometer and airway, under stirring
Glycidyl methacrylate is slowly added to, after swelling 10-13 hours, SiO is added2Prevent polrvinyl chloride from luming, continue to stir
Mix to uniform, then chlorine displacement system air is passed through under stirring, room temperature, is warming up to 110-122 DEG C, reacts 20-30 minutes,
Stop logical chlorine and stop evacuation after heating, when being cooled to less than 100 DEG C, displaced air 3-4 time is slow by reactant liquor while hot
Pour in the beaker for filling acetone and methanol mixed solution and precipitate, stirred with Glass rod in precipitation, sucking filtration obtains filter cake, will
Filter cake is smashed to pieces, is placed on 50-60 DEG C and is dried under vacuum to constant weight, obtains graft product PVC-cg-GMA；
（2）PVC-cg-GMA is grafted the preparation of brucite：
Brucite is added in dimethyl sulfoxide and is stirred 8-15 minutes, afterwards ultrasonic disperse 10-25 minutes, after being uniformly dispersed, plus
Enter step（1）PVC-cg-GMA, after mixing is stirred at room temperature, then the dropwise dimethyl sulphoxide solution of instillation butter of tin, instead
Answer 20-40 minutes, after reaction terminates, washing obtains PVC-cg-GMA grafting brucites；
（3）The preparation of modified nano-titanium dioxide：
Ferric nitrate, nano titanium oxide are added in deionized water, are stirred at room temperature 2-3 days, are then aged 25-30 little
When, it is dried, 2-4 hours is calcined at 470-490 DEG C after grinding, calcining is cooled to room temperature and obtains modified nano-silica after terminating
Titanium；
（4）Premix：
Start homogenizer and be heated to 55-75 DEG C, by step（2）PVC-cg-GMA grafting brucites, organotin are thermally-stabilised
Agent, chlorinated polyethylene are sequentially added in homogenizer, are heated to 95-110 DEG C while stirring, add step afterwards（3）Prepare
Modified nano-titanium dioxide, Zinc Oxide, dioctyl phthalate, finally add OPE, after stirring,
60 DEG C are cooled to bottom discharge, then carry out it is cold mixed, after the completion of obtain pre-composition；
（5）Extrusion, injection：
By step（4）Pre-composition be added in extruder, through melting, plasticizing, mix from the head of extruder and continuously extrude
Material, after the completion of obtain extrusioning mixture, mixture is molded into into standard specimen using injection machine afterwards, product is obtained.
Wherein, described step（1）Middle acetone and methanol mixed solution are with volume ratio as 1 by acetone with methanol:1 mixing
Form.
Wherein, described step（5）Middle extruder setup parameter is as follows：Screw speed is 13-16r/min, charging rate
For 45-50mm/s, pressure is 70Mpa, and extruder feeding section temperature is set as 165-175 DEG C, 175-185 DEG C of mixing section, metering
180-190 DEG C of section, head section 180-185 DEG C.
Compared with prior art, the present invention has advantages below：
（1）Containing the dilute base of second dialled living and the epoxy for having ionic reaction in the glycidyl methacrylate that the present invention is used
, there is double bond when in-situ chlorinated graft method reacts PVC-cg-GMA processed with polrvinyl chloride and participate in reaction in the Liang Ge functional groups of base so that
Epoxide group is located on side chain, is reacted with brucite afterwards, the hydroxyl radical attacks epoxy radicals of hydrotalcite surface under catalyst action
There is additive reaction in group, brucite is grafted on PVC-cg-GMA skeletons, generate PVC-cg-GMA grafting hydrotalcite complexes.
（2）After the present invention is to the graft modification of brucite, the lipophile of brucite and compatible with polrvinyl chloride is improve
Property so as to uniform dispersion can be reached in PVC base system, brucite pair is effectively played with organo-tin het stabilizer compounding
The heat stability of polrvinyl chloride, weather resistance, in addition the impact strength and tensile strength of material also improve, reach enhancing
Effect.
（3）The present invention has synthesized Fe with ferric nitrate and nano titanium oxide as raw material3+The nano titanium oxide of doping, with
Zinc Oxide, brucite coordinate, and the growth to multiple-microorganism and mushroom has significant inhibitory action, high with effective sterilization component
The features such as degree dispersion, sterilization of high efficiency, give tubing excellent antibiotic property.
Specific embodiment
A kind of antimicrobial form brucite graft modification polyvinyl chloride composite pipe, is made up of the raw material of following weight portion：Polychlorostyrene
Ethylene 80, glycidyl methacrylate 10, SiO2 3, acetone in proper, appropriate methanol, brucite 14, dimethyl sulfoxide 48,
Butter of tin 0.7, organo-tin het stabilizer 2, chlorinated polyethylene 7, OPE 2, dioctyl phthalate 3, nitric acid
Ferrum 4, nano titanium oxide 9, appropriate deionized water, Zinc Oxide 3.
Comprise the following steps that：
（1）Polyvinyl chloride graft glycidyl methacrylate（PVC-cg-GMA）Preparation：
Pre-dried polrvinyl chloride is added in the there-necked flask equipped with agitator, thermometer and airway, under stirring
It is slowly added to glycidyl methacrylate, after swelling 12 hours, adds SiO2Prevent polrvinyl chloride from luming, continue stirring extremely
Uniformly, then chlorine displacement system air is passed through under stirring, room temperature, be warming up to 115 DEG C, react 25 minutes, stop logical chlorine
And stopping evacuation after heating, when being cooled to less than 100 DEG C, reactant liquor is slowly poured into and fills third by displaced air 3 times while hot
Precipitate in the beaker of ketone and methanol mixed solution, stirred with Glass rod in precipitation, sucking filtration obtains filter cake, filter cake is smashed to pieces, puts
Constant weight is dried under vacuum at 55 DEG C, graft product PVC-cg-GMA is obtained；
（2）PVC-cg-GMA is grafted the preparation of brucite：
Brucite is added and stir in dimethyl sulfoxide 10 minutes, ultrasonic disperse 20 minutes, after being uniformly dispersed, add step afterwards
（1）PVC-cg-GMA, after mixing is stirred at room temperature, then the dropwise dimethyl sulphoxide solution of instillation butter of tin, react 30 points
Clock, after reaction terminates, washing obtains PVC-cg-GMA grafting brucites；
（3）The preparation of modified nano-titanium dioxide：
Ferric nitrate, nano titanium oxide are added in deionized water, are stirred at room temperature 2.5 days, are then aged 28 hours, do
Calcine 3 hours at 480 DEG C after dry, grinding, calcining is cooled to room temperature after terminating and obtains modified nano-titanium dioxide；
（4）Premix：
Start homogenizer and be heated to 65 DEG C, by step（2）PVC-cg-GMA grafting brucite, organo-tin het stabilizer,
Chlorinated polyethylene is sequentially added in homogenizer, is heated to 100 DEG C while stirring, adds step afterwards（3）What is prepared is modified
Nano titanium oxide, Zinc Oxide, dioctyl phthalate, finally add OPE, after stirring, are cooled to
60 DEG C with bottom discharge, then carry out it is cold mixed, after the completion of obtain pre-composition；
（5）Extrusion, injection：
By step（4）Pre-composition be added in extruder, through melting, plasticizing, mix from the head of extruder and continuously extrude
Material, after the completion of obtain extrusioning mixture, mixture is molded into into standard specimen using injection machine afterwards, product is obtained.
Wherein, described step（1）Middle acetone and methanol mixed solution are with volume ratio as 1 by acetone with methanol:1 mixing
Form.
Wherein, described step（5）Middle extruder setup parameter is as follows：Screw speed is 15r/min, and charging rate is
48mm/s, pressure is 70Mpa, and extruder feeding section temperature is set as 170 DEG C, 180 DEG C of mixing section, 185 DEG C of metering section, head section
182℃。
The performance test results are as follows：
Tensile strength：45.1MPa, bending strength：83MPa, impact strength are 79.2KJ/m2, vicat softening temperature（1Kg bears
Lotus）：81.8℃.
Claims (4)
1. a kind of antimicrobial form brucite graft modification polyvinyl chloride composite pipe, it is characterised in that by the raw material of following weight portion
Composition：Polrvinyl chloride 70-90 parts, glycidyl methacrylate 6-12 part, SiO2 2-5 parts, acetone in proper, appropriate methanol,
Brucite 10-16 parts, dimethyl sulfoxide 40-60 parts, butter of tin 0.3-1 parts, organo-tin het stabilizer 1-2 parts, chlorinated polyethylene
Alkene 5-9 parts, OPE 1-3 parts, dioctyl phthalate 2-4 parts, ferric nitrate 3-5 parts, nano titanium oxide 6-12
Part, appropriate deionized water, Zinc Oxide 1-4 part.
2. the preparation side of a kind of antimicrobial form brucite graft modification polyvinyl chloride composite pipe according to claims 1
Method, it is characterised in that comprise the following steps that：
（1）Polyvinyl chloride graft glycidyl methacrylate（PVC-cg-GMA）Preparation：
Pre-dried polrvinyl chloride is added in the there-necked flask equipped with agitator, thermometer and airway, under stirring
Glycidyl methacrylate is slowly added to, after swelling 10-13 hours, SiO is added2Prevent polrvinyl chloride from luming, continue to stir
Mix to uniform, then chlorine displacement system air is passed through under stirring, room temperature, is warming up to 110-122 DEG C, reacts 20-30 minutes,
Stop logical chlorine and stop evacuation after heating, when being cooled to less than 100 DEG C, displaced air 3-4 time is slow by reactant liquor while hot
Pour in the beaker for filling acetone and methanol mixed solution and precipitate, stirred with Glass rod in precipitation, sucking filtration obtains filter cake, will
Filter cake is smashed to pieces, is placed on 50-60 DEG C and is dried under vacuum to constant weight, obtains graft product PVC-cg-GMA；
（2）PVC-cg-GMA is grafted the preparation of brucite：
Brucite is added in dimethyl sulfoxide and is stirred 8-15 minutes, afterwards ultrasonic disperse 10-25 minutes, after being uniformly dispersed, plus
Enter step（1）PVC-cg-GMA, after mixing is stirred at room temperature, then the dropwise dimethyl sulphoxide solution of instillation butter of tin, instead
Answer 20-40 minutes, after reaction terminates, washing obtains PVC-cg-GMA grafting brucites；
（3）The preparation of modified nano-titanium dioxide：
Ferric nitrate, nano titanium oxide are added in deionized water, are stirred at room temperature 2-3 days, are then aged 25-30 little
When, it is dried, 2-4 hours is calcined at 470-490 DEG C after grinding, calcining is cooled to room temperature and obtains modified nano-silica after terminating
Titanium；
（4）Premix：
Start homogenizer and be heated to 55-75 DEG C, by step（2）PVC-cg-GMA grafting brucites, organotin are thermally-stabilised
Agent, chlorinated polyethylene are sequentially added in homogenizer, are heated to 95-110 DEG C while stirring, add step afterwards（3）Prepare
Modified nano-titanium dioxide, Zinc Oxide, dioctyl phthalate, finally add OPE, after stirring,
60 DEG C are cooled to bottom discharge, then carry out it is cold mixed, after the completion of obtain pre-composition；
（5）Extrusion, injection：
By step（4）Pre-composition be added in extruder, through melting, plasticizing, mix from the head of extruder and continuously extrude
Material, after the completion of obtain extrusioning mixture, mixture is molded into into standard specimen using injection machine afterwards, product is obtained.
3. the preparation side of a kind of antimicrobial form brucite graft modification polyvinyl chloride composite pipe according to claims 2
Method, it is characterised in that described step（1）Middle acetone and methanol mixed solution are with volume ratio as 1 by acetone with methanol:1 mixes
Conjunction is formed.
4. the preparation side of a kind of antimicrobial form brucite graft modification polyvinyl chloride composite pipe according to claims 2
Method, it is characterised in that described step（5）Middle extruder setup parameter is as follows：Screw speed is 13-16r/min, charging rate
For 45-50mm/s, pressure is 70Mpa, and extruder feeding section temperature is set as 165-175 DEG C, 175-185 DEG C of mixing section, metering
180-190 DEG C of section, head section 180-185 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611007847.8A CN106589972A (en) | 2016-11-16 | 2016-11-16 | Antibacterial hydrotalcite grafting-modified polyvinyl chloride composite pipe material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611007847.8A CN106589972A (en) | 2016-11-16 | 2016-11-16 | Antibacterial hydrotalcite grafting-modified polyvinyl chloride composite pipe material and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN106589972A true CN106589972A (en) | 2017-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611007847.8A Withdrawn CN106589972A (en) | 2016-11-16 | 2016-11-16 | Antibacterial hydrotalcite grafting-modified polyvinyl chloride composite pipe material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028938A (en) * | 2022-07-08 | 2022-09-09 | 广东美橙文化发展有限公司 | Ag/ZnO modified polyvinyl chloride composite antibacterial plastic and synthesis process thereof |
-
2016
- 2016-11-16 CN CN201611007847.8A patent/CN106589972A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028938A (en) * | 2022-07-08 | 2022-09-09 | 广东美橙文化发展有限公司 | Ag/ZnO modified polyvinyl chloride composite antibacterial plastic and synthesis process thereof |
| CN115028938B (en) * | 2022-07-08 | 2024-01-30 | 广东金丰塑料制品有限公司 | Ag/ZnO modified polyvinyl chloride composite antibacterial plastic and synthesis process thereof |
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