CN106751323A - A kind of poly- modified vinyl chloride plastic tubing of low temperature resistant anti-freezing type hydrotalcite grafting and preparation method thereof - Google Patents

A kind of poly- modified vinyl chloride plastic tubing of low temperature resistant anti-freezing type hydrotalcite grafting and preparation method thereof Download PDF

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Publication number
CN106751323A
CN106751323A CN201611007830.2A CN201611007830A CN106751323A CN 106751323 A CN106751323 A CN 106751323A CN 201611007830 A CN201611007830 A CN 201611007830A CN 106751323 A CN106751323 A CN 106751323A
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parts
gma
hydrotalcite
grafting
pvc
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Inventor
吴传兴
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Maanshan Jiechuang Plastic Science & Technology Co Ltd
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Maanshan Jiechuang Plastic Science & Technology Co Ltd
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Priority to CN201611007830.2A priority Critical patent/CN106751323A/en
Publication of CN106751323A publication Critical patent/CN106751323A/en
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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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • 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
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of low temperature resistant poly- modified vinyl chloride plastic tubing of anti-freezing type hydrotalcite grafting, it is made up of the raw material of following weight portion：70 90 parts of polyvinyl chloride, 7 14 parts of GMA, SiO2 25 parts, acetone in proper, appropriate methyl alcohol, 12 20 parts of hydrotalcite, 45 68 parts of dimethyl sulfoxide (DMSO), 0.3 1 parts of butter of tin, 12 parts of organo-tin het stabilizer, 48 parts of haloflex, 23 parts of OPE, 24 parts of dioctyl phthalate, 25 parts of ethylene glycol, 24 parts of antioxidant, 13 parts of paraffin.The present invention prepares graft product PVC cg GMA using polyvinyl chloride and GMA situ-formed graft, afterwards using the epoxide group and hydrotalcite graft reaction of GMA, heat endurance, the weather resistance of polychloroethylene pipes are improve, while having excellent mechanical property.

Description

A kind of low temperature resistant anti-freezing type hydrotalcite grafting poly- modified vinyl chloride plastic tubing and its system Preparation Method
Technical field
The present invention relates to the technology of preparing of polychloroethylene pipes, and in particular to a kind of low temperature resistant anti-freezing type hydrotalcite grafting is poly- Modified vinyl chloride plastic tubing and preparation method thereof.
Background technology
Polychloroethylene pipes occupy an important position in numerous plastic pipes, and it has light weight, acid-alkali-corrosive-resisting, defeated Resistance is small when sending fluid, insulating properties is excellent, construction is rapid easily, long service life, secondary operation are convenient, raw material sources fill Sufficient, cheap the advantages of, it is widely used in the fields such as work, agricultural production and daily life.However, polyvinyl chloride itself Existing defects and deficiency, such as heat endurance are poor, and plasticization is unstable, volatile migration, and boardy product is in fragility, shock resistance Difference etc..
Meng Li, Zhao Jiruo et al. are at it《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 used in one text by PVC and GMA (GMA) graft-blending, Zhi Houli Crosslink poly (glycidyl methacrylate) to form cross-linked network and mutually passed through with PVC linear macromolecule chains with hexamethylene diamine Wear, prepare the semi-interpenetrating network polymer with PVC as matrix, improve dynamic mechanical and heat endurance of PVC etc..
Hydrotalcite can be decomposed with polyvinyl chloride and produce HCl to react, and can play heat stabilization to polyvinyl chloride, And hydrotalcite and some other thermally-stabilised auxiliary agent compound tense, heat stabilization is more obvious；In the absorbable sunshine of hydrotalcite Ultraviolet, and be translated into heat and discharge, reduce polyvinyl chloride and be subject to the direct irradiation of intense UV rays and degrade Possibility, improves weatherability；Hydrotalcite contains and combines water, and with veneer structure, can absorb what polyvinyl chloride burning was released Heat, suppresses the generation of smog, improves anti-flammability；Therefore, hydrotalcite be a kind of excellent, multi-functional polyvinyl chloride auxiliary agent or Modifying agent.
Therefore the present invention prepares graft product PVC- using polyvinyl chloride and GMA situ-formed graft Cg-GMA, afterwards using the epoxide group and hydrotalcite graft reaction of GMA, improves polyvinyl chloride The heat endurance of tubing, weather resistance, while having excellent mechanical property.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of low temperature resistant anti-freezing type hydrotalcite grafting poly- modified vinyl chloride modeling Expects pipe material and preparation method thereof.
A kind of poly- modified vinyl chloride plastic tubing of low temperature resistant anti-freezing type hydrotalcite grafting, by the raw material group of following weight portion Into：Polyvinyl chloride 70-90 parts, GMA 7-14 parts, SiO2 2-5 parts, acetone in proper, appropriate methyl alcohol, water Talcum 12-20 parts, dimethyl sulfoxide (DMSO) 45-68 parts, butter of tin 0.3-1 parts, organo-tin het stabilizer 1-2 parts, haloflex 4-8 parts, OPE 2-3 parts, dioctyl phthalate 2-4 parts, ethylene glycol 2-5 parts, antioxidant 2-4 parts, paraffin 1-3 Part.
Comprise the following steps that：
（1）Polyvinyl chloride graft GMA（PVC-cg-GMA）Preparation：
Pre-dried polyvinyl chloride is added in the there-necked flask equipped with agitator, thermometer and wireway, under stirring GMA is slowly added to, after swelling 10-13 hours, SiO is added2Prevent polyvinyl chloride from luming, continue to stir Mix to uniform, chlorine displacement system air be then passed through under stirring, normal temperature, be warming up to 110-122 DEG C, react 20-30 minutes, Stop logical chlorine and vacuumized after stopping heating, be cooled to during less than 100 DEG C, displaced air 3-4 times is slow by reaction solution while hot Pour into the beaker for filling acetone and methyl alcohol mixed solution and precipitate, stirred with glass bar in precipitation, suction 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 hydrotalcite：
Will hydrotalcite add dimethyl sulfoxide (DMSO) in stir 8-15 minutes, ultrasonic disperse 10-25 minutes afterwards, 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 hydrotalcites；
（3）Premix：
Start homogenizer and be heated to 55-75 DEG C, by step（2）PVC-cg-GMA grafting hydrotalcite, organotin are thermally-stabilised Agent, haloflex, ethylene glycol are sequentially added in homogenizer, and 95-110 DEG C is heated to while stirring, and adjacent benzene is added afterwards Diformazan dioctyl phthalate, antioxidant, paraffin, finally add OPE, after stirring, are cooled to less than 60 DEG C and go out Material, then carry out it is cold mixed, after the completion of obtain pre-composition；
（4）Extrusion, injection：
By step（3）Pre-composition be added in extruder, by melting, plasticizing, mix and continuously extruded from the head of extruder Material, after the completion of obtain extrusioning mixture, mixture is molded into standard specimen using injection machine afterwards, obtain product.
Wherein, described step（1）Middle acetone and methyl alcohol mixed solution be by acetone and methyl alcohol with volume ratio be 1:1 mixing Form.
Wherein, described step（4）Middle extruder setup parameter is as follows：Screw speed is 13-16r/min, charging rate It is 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, 180-185 DEG C of head section.
Compared with prior art, the present invention has advantages below：
（1）Contain the dilute base of second dialled living and the epoxy for having ionic reaction in the GMA that the present invention is used , there is double bond when in-situ chlorinated graft method reacts PVC-cg-GMA processed with polyvinyl 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 hydrotalcite afterwards, the hydroxyl radical attacks epoxy radicals of hydrotalcite surface under catalyst action There is addition reaction in group, hydrotalcite is grafted on PVC-cg-GMA skeletons, generation PVC-cg-GMA grafting hydrotalcite complexes.
（2）After the present invention is to the graft modification of hydrotalcite, the lipophile of hydrotalcite and compatible with polyvinyl chloride is improve Property, uniform dispersion can be reached in PVC base system, effectively play hydrotalcite pair with organo-tin het stabilizer compounding The heat endurance of polyvinyl chloride, weather resistance, in addition the impact strength and tensile strength of material also improve, reach enhancing Effect.
（3）Coordinate as antifreeze and antioxidant present invention uses ethylene glycol, polyvinyl chloride pipe can be effectively protected Material will not cause that tubing is broken because of bad environments, and especially lower temperature resistance is good, be not easy to fracture, breakage under cryogenic conditions Deng.
Specific embodiment
A kind of poly- modified vinyl chloride plastic tubing of low temperature resistant anti-freezing type hydrotalcite grafting, by the raw material group of following weight portion Into：Polyvinyl chloride 80, GMA 11, SiO2 3, acetone in proper, appropriate methyl alcohol, hydrotalcite 17, dimethyl Sulfoxide 50, butter of tin 0.8, organo-tin het stabilizer 2, haloflex 6, OPE 2, dioctyl phthalate 3, ethylene glycol 3, antioxidant 3, paraffin 2.
Comprise the following steps that：
（1）Polyvinyl chloride graft GMA（PVC-cg-GMA）Preparation：
Pre-dried polyvinyl chloride is added in the there-necked flask equipped with agitator, thermometer and wireway, under stirring It is slowly added to GMA, after swelling 12 hours, adds SiO2Prevent polyvinyl chloride from luming, continue to stir extremely Uniformly, chlorine displacement system air is then passed through under stirring, normal temperature, 115 DEG C are warming up to, is reacted 25 minutes, stop logical chlorine And vacuumized after stopping heating, it is cooled to during less than 100 DEG C, reaction solution is slowly poured into fill third while hot by displaced air 3 times Precipitated in the beaker of ketone and methyl alcohol mixed solution, stirred with glass bar in precipitation, suction 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 hydrotalcite：
Stirred 10 minutes during hydrotalcite is added into dimethyl sulfoxide (DMSO), 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 hydrotalcites；
（3）Premix：
Start homogenizer and be heated to 65 DEG C, by step（2）PVC-cg-GMA grafting hydrotalcite, organo-tin het stabilizer, Haloflex, ethylene glycol are sequentially added in homogenizer, and 100 DEG C are heated to while stirring, and phthalic acid is added afterwards Dioctyl ester, antioxidant, paraffin, finally add OPE, after stirring, are cooled to 60 DEG C with bottom discharge, then enter Row is cold mixed, after the completion of obtain pre-composition；
（4）Extrusion, injection：
By step（3）Pre-composition be added in extruder, by melting, plasticizing, mix and continuously extruded from the head of extruder Material, after the completion of obtain extrusioning mixture, mixture is molded into standard specimen using injection machine afterwards, obtain product.
Wherein, described step（1）Middle acetone and methyl alcohol mixed solution be by acetone and methyl alcohol with volume ratio be 1:1 mixing Form.
Wherein, described step（4）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：44.7MPa, bending strength：83MPa, impact strength is 79.2KJ/m2, vicat softening temperature（1Kg bears Lotus）：81.6℃.

Claims (4)

1. a kind of low temperature resistant anti-freezing type hydrotalcite grafting gathers modified vinyl chloride plastic tubing, it is characterised in that by following weight portion Raw material composition：Polyvinyl chloride 70-90 parts, GMA 7-14 parts, SiO2 2-5 parts, acetone in proper, methyl alcohol In right amount, hydrotalcite 12-20 parts, dimethyl sulfoxide (DMSO) 45-68 parts, butter of tin 0.3-1 parts, organo-tin het stabilizer 1-2 parts, chlorination Polyethylene 4-8 parts, OPE 2-3 parts, dioctyl phthalate 2-4 parts, ethylene glycol 2-5 parts, antioxidant 2-4 parts, Paraffin 1-3 parts.
2. the system of the poly- modified vinyl chloride plastic tubing of a kind of low temperature resistant anti-freezing type hydrotalcite grafting according to claims 1 Preparation Method, it is characterised in that comprise the following steps that：
（1）Polyvinyl chloride graft GMA（PVC-cg-GMA）Preparation：
Pre-dried polyvinyl chloride is added in the there-necked flask equipped with agitator, thermometer and wireway, under stirring GMA is slowly added to, after swelling 10-13 hours, SiO is added2Prevent polyvinyl chloride from luming, continue to stir Mix to uniform, chlorine displacement system air be then passed through under stirring, normal temperature, be warming up to 110-122 DEG C, react 20-30 minutes, Stop logical chlorine and vacuumized after stopping heating, be cooled to during less than 100 DEG C, displaced air 3-4 times is slow by reaction solution while hot Pour into the beaker for filling acetone and methyl alcohol mixed solution and precipitate, stirred with glass bar in precipitation, suction 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 hydrotalcite：
Will hydrotalcite add dimethyl sulfoxide (DMSO) in stir 8-15 minutes, ultrasonic disperse 10-25 minutes afterwards, 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 hydrotalcites；
（3）Premix：
Start homogenizer and be heated to 55-75 DEG C, by step（2）PVC-cg-GMA grafting hydrotalcite, organotin are thermally-stabilised Agent, haloflex, ethylene glycol are sequentially added in homogenizer, and 95-110 DEG C is heated to while stirring, and adjacent benzene is added afterwards Diformazan dioctyl phthalate, antioxidant, paraffin, finally add OPE, after stirring, are cooled to less than 60 DEG C and go out Material, then carry out it is cold mixed, after the completion of obtain pre-composition；
（4）Extrusion, injection：
By step（3）Pre-composition be added in extruder, by melting, plasticizing, mix and continuously extruded from the head of extruder Material, after the completion of obtain extrusioning mixture, mixture is molded into standard specimen using injection machine afterwards, obtain product.
3. the system of the poly- modified vinyl chloride plastic tubing of a kind of low temperature resistant anti-freezing type hydrotalcite grafting according to claims 2 Preparation Method, it is characterised in that described step（1）Middle acetone and methyl alcohol mixed solution be by acetone and methyl alcohol with volume ratio be 1: 1 mixes.
4. the system of the poly- modified vinyl chloride plastic tubing of a kind of low temperature resistant anti-freezing type hydrotalcite grafting according to claims 2 Preparation Method, it is characterised in that described step（4）Middle extruder setup parameter is as follows：Screw speed is 13-16r/min, charging Speed is 45-50mm/s, and pressure is 70Mpa, and extruder feeding section temperature is set as 165-175 DEG C, 175-185 DEG C of mixing section, 180-190 DEG C of metering section, 180-185 DEG C of head section.
CN201611007830.2A 2016-11-16 2016-11-16 A kind of poly- modified vinyl chloride plastic tubing of low temperature resistant anti-freezing type hydrotalcite grafting and preparation method thereof Withdrawn CN106751323A (en)

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CN201611007830.2A CN106751323A (en) 2016-11-16 2016-11-16 A kind of poly- modified vinyl chloride plastic tubing of low temperature resistant anti-freezing type hydrotalcite grafting and preparation method thereof

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Application Number Priority Date Filing Date Title
CN201611007830.2A CN106751323A (en) 2016-11-16 2016-11-16 A kind of poly- modified vinyl chloride plastic tubing of low temperature resistant anti-freezing type hydrotalcite grafting and preparation method thereof

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CN106751323A true CN106751323A (en) 2017-05-31

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Application publication date: 20170531