CN102911451B - High-impact PVC (polyvinyl chloride)/ABS (poly(acrylonitrile butadiene styrene))/alpha-SAN(alpha-styrene acrylonitrile copolymer) tubing and preparation method thereof - Google Patents

High-impact PVC (polyvinyl chloride)/ABS (poly(acrylonitrile butadiene styrene))/alpha-SAN(alpha-styrene acrylonitrile copolymer) tubing and preparation method thereof Download PDF

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CN102911451B
CN102911451B CN201210357247.XA CN201210357247A CN102911451B CN 102911451 B CN102911451 B CN 102911451B CN 201210357247 A CN201210357247 A CN 201210357247A CN 102911451 B CN102911451 B CN 102911451B
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tubing
abs
san
powder
alpha
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CN102911451A (en
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林传忍
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Nantong Qianqianhui Need Chemical Co ltd
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GUANYI INDUSTRIAL Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/78Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885Screw or gear
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

Abstract

The invention discloses a high-impact PVC (polyvinyl chloride)/ABS (poly(acrylonitrile butadiene styrene))/alpha-SAN(styrene acrylonitrile copolymer) tubing and a preparation method thereof. The tubing is prepared from a material A and a material B by steps of proportionally mixing, extruding and granulating. Since a formula is optimized further, dispersing of organic packing can be improved during processing of the PVC tubing, fluidity of PVC melt can be improved, tensile strength and elongation at break can be improved, and the defect of good ductility but low hardness of polyethylene products produced by utilizing chlorinated polyethylene is overcome. In addition, since components such as impact modifiers ACR, ACM (poly(acrylic acid ester rubber)), alpha-SAN (alpha-styrene acrylonitrile copolymer) resin and ABS (poly(acrylonitrile butadiene styrene)) resin are utilized in the formula, cold bending performance and impact resistance of the tubing produced according to the formula are improved.

Description

A kind of high-impact PVC/ABS/ α-SAN tubing and preparation method thereof
Technical field
The present invention relates to PVC production field, particularly relate to a kind of high-impact PVC/ABS/ α-SAN tubing and preparation method thereof.
Background technology
The major ingredient of PVC is polyvinyl chloride, adds the auxiliary material such as softening agent, antiaging agent in addition to increase its thermotolerance, toughness, ductility etc.PVC be the world today is liked deeply, the rather popular and a kind of synthetic materials be also widely used.PVC is a kind of tubing of maturation, is mainly used in water supply and sewage work.PVC has acidproof, alkaline-resisting, erosion resistance, intensity advantages of higher, but, at present large step point production manufacturer production PVC shock resistance out bad, especially the plasticizing process in the processing of PVC product, the dispersion of inorganics and the processing fluidity of PVC melt are difficult problems always.
Summary of the invention
The object of the invention is to provide a kind of high-impact PVC/ABS/ α-SAN tubing and preparation method thereof for the deficiencies in the prior art, improve the shock resistance of PVC.
For achieving the above object, the present invention adopts following technical scheme:
A kind of high-impact PVC/ABS/ α-SAN tubing is expected by A and B expects that equal proportion mixes extruding pelletization and is prepared from, and described A material, B material are obtained by the raw material extruding pelletization of following weight part respectively:
A expects:
Polyvinyl chloride SG-5 50-60, polyvinyl chloride reworked material 40-50, Calcium of intensifiens 20-30, chlorinatedpolyethylene 10-20, ABS high glue powder 5-10, dimethyl dimercapto 2-ethyl hexyl ethanoate tin 2-5, diisopropyl azodiformate 0.2-0.4, impact modifier ACR 5-10, vinyltriethoxysilane 0.3-0.5, oxidation inhibitor 1035 0.4-0.6, pentanoic 0.2-0.4, ethylene bis stearamide 0.3-0.5, two ten four carbon alcohols ester 0.1-0.2, modified Nano powder 5-10
Described modified Nano powder is obtained by following method: after calcium carbonate, celestite powder, the mixing of limestone powder equal proportion, scaling loss 4-5 hour at 600-700 DEG C, then nanometer powder is ground to form, admix the Di(dioctylpyrophosphato) ethylene titanate agitating being equivalent to powder weight 3-5% even, dry, be ground into powder;
B expects:
Polyvinyl chloride SG-5 50-60, ABS resin 20-30, α-SAN resin 20-30, poly-4-methyl-1-pentene 10-15, ACM 4-8, Cellmic C 121 2-5, chlorinatedpolyethylene 10-20, tetra isopropyl two (dioctyl phosphito acyloxy) titanic acid ester 0.3-0.5, two octadecanol ester 0.1-0.3, antioxidant 618 0.2-0.5, oxidized polyethlene wax 0.3-0.5, Zinic stearas 2-5, clorafin 1-3, modified coal ash 5-10
Described modified coal ash is made up of following method: the flyash after calcination is successively placed in 20-25% sulfuric acid, 16-24% sodium hydroxide solution successively, stir 20-22h, then the flyash leached from soda acid immersion liquid, with deionized water rinsing to neutral, and determined with the test of PH test paper, finally filter, dry, then flyash is pressed: wollastonite powder: three kinds of materials are sent into 1050-1100 DEG C of roasting 1-1.5 hour in fluidized-bed by ground dolomite weight ratio 1:0.3-0.5:0.5-0.8, grind to form nanometer powder after cooling.
The preparation method of described high-impact PVC/ABS/ α-SAN tubing comprises the following steps:
The first step: prepare A material, B material respectively
One, the preparation of A material
(1) take each formula material by formula rate, the starting material weighed up are dropped into high-speed stirring 10-15 min in high-speed mixer, and temperature is 80-90 DEG C, after its moisture content fully evaporates, through cold mixer, material is down to 40-50 DEG C;
(2) above-mentioned compound is joined in parallel double-screw extruder carry out melt blending and granulation namely obtain A material, extruder barrel temperature is 245-255 DEG C, and die head temperature is 252-268 DEG C, and screw speed is 300-550rpm;
Two, the preparation of B material
The preparation of B material adopts the identical technique with A material to carry out granulation;
Second step: A expects to expect mixing granulation with B
Above-mentioned obtained A expected and B material equal proportion joins in parallel double-screw extruder and carries out melt blending and namely granulation obtains stuff and other stuff, extruder barrel temperature is 265-275 DEG C, and die head temperature is 272-286 DEG C, and screw speed is 300-550rpm;
3rd step: extrusion moulding
Adopt conical double screw extruder by the stuff and other stuff extrusion moulding of gained, obtain high-impact PVC/ABS/ α-SAN tubing, extruder barrel temperature is 276-298 DEG C, and die head temperature is 282-305 DEG C;
4th step: aftertreatment
The high-impact PVC/ABS/ α-SAN tubing of gained is cooled to 5-10 DEG C of sizings, then the tubing of sizing is cut by necessary requirement, finally the product of well cutting is packed, put into warehouse as ready.
The present invention has following beneficial effect:
The present invention, by optimizing further formula, makes the dispersion that can promote mineral filler in the course of processing of PVC, improves the mobility of PVC melt, tensile strength and elongation at break can also be promoted, change polyethylene products when using chlorinatedpolyethylene, good toughness, the shortcoming that hardness is low; In the present invention's formula after the compositions such as use impact modifier ACR, ACM, α-SAN resin, ABS resin, the cold-bending property of the tubing produced, impact resistance all increases.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment
The preparation method of high-impact PVC/ABS/ α-SAN tubing comprises the following steps:
The preparation that the first step: A expects
Take off the raw material of row weight part: polyvinyl chloride SG-5 60, polyvinyl chloride reworked material 40, Calcium of intensifiens 30, chlorinatedpolyethylene 20, ABS high glue powder 10, dimethyl dimercapto 2-ethyl hexyl ethanoate tin 5, diisopropyl azodiformate 0.4, impact modifier ACR 10, vinyltriethoxysilane 0.5, oxidation inhibitor 1,035 0.6, pentanoic 0.4, ethylene bis stearamide 0.5, two ten four carbon alcohols esters 0.2, modified Nano powder 10
Wherein, modified Nano powder is obtained by following method: after calcium carbonate, celestite powder, the mixing of limestone powder equal proportion, scaling loss 5 hours at 650 DEG C, then nanometer powder is ground to form, admix the Di(dioctylpyrophosphato) ethylene titanate agitating being equivalent to powder weight 4% even, dry, be ground into powder
The starting material weighed up are dropped into high-speed stirring 15 min in high-speed mixer, temperature is 90 DEG C, after its moisture content fully evaporates, through cold mixer, material is down to 40 DEG C, above-mentioned compound is joined in parallel double-screw extruder carry out melt blending and granulation namely obtain A material, extruder barrel temperature is 254 DEG C, and die head temperature is 264 DEG C, and screw speed is 350rpm;
The preparation that second step: B expects
Take off the raw material of row weight part: polyvinyl chloride SG-5 50, ABS resin 20, α-SAN resin 30, poly-4-methyl-1-pentene 15, ACM 6, Cellmic C 121 4, chlorinatedpolyethylene 15, tetra isopropyl two (dioctyl phosphito acyloxy) titanic acid ester 0.5, two octadecanol ester 0.3, antioxidant 618 0.4, oxidized polyethlene wax 0.4, Zinic stearas 5, clorafin 2, modified coal ash 8
Wherein, modified coal ash is made up of following method: the flyash after calcination is successively placed in 20% sulfuric acid, 20% sodium hydroxide solution successively, stir 20h, the flyash then leached from soda acid immersion liquid, with deionized water rinsing to neutral, and determined with the test of PH test paper, finally filter, dry, then press flyash: wollastonite powder: ground dolomite weight ratio 1:0.4:0.6 was by 1080 DEG C of roastings in three kinds of materials feeding fluidized-beds 1 hour, nanometer powder is ground to form after cooling
The starting material weighed up are dropped into high-speed stirring 15 min in high-speed mixer, temperature is 90 DEG C, after its moisture content fully evaporates, through cold mixer, material is down to 40 DEG C, above-mentioned compound is joined in parallel double-screw extruder carry out melt blending and granulation namely obtain B material, extruder barrel temperature is 254 DEG C, and die head temperature is 264 DEG C, and screw speed is 350rpm;
3rd step: A expects to expect mixing granulation with B
Above-mentioned obtained A expected and B material equal proportion joins in parallel double-screw extruder and carries out melt blending and namely granulation obtains stuff and other stuff, extruder barrel temperature is 272 DEG C, and die head temperature is 285 DEG C, and screw speed is 400rpm;
4th step: extrusion moulding
Adopt conical double screw extruder by the stuff and other stuff extrusion moulding of gained, obtain high-impact PVC/ABS/ α-SAN tubing, extruder barrel temperature is 285 DEG C, and die head temperature is 298 DEG C;
5th step: aftertreatment
The high-impact PVC/ABS/ α-SAN tubing of gained is cooled to 5 DEG C of sizings, then the tubing of sizing is cut by necessary requirement, finally the product of well cutting is packed, put into warehouse as ready.
Contrast verification test result of the present invention is as following table:
Sequence number Test item and unit QB/T2480 index Common PVC tubing Sample in this enforcement
1 Outward appearance Inside and outside wall should be smooth, without surface imperfection such as depression and decomposition variable color lines Inside and outside wall is smooth, without surface imperfection such as depression and decomposition variable color lines Inside and outside wall is smooth, without surface imperfection such as depression and decomposition variable color lines
2 Tensile strength, Mpa ≥43 45 58
3 Elongation at break, % ≥80 108 114
4 Longitudinal welds, % ≤3.5 3.0 1.8
5 Vicat softening temperature, DEG C ≥75 81 92
6 Falling weight impact test (20 DEG C, 2kg, 2m), TIR ≤10% 6 1
As can be seen from the above table, compared with common PVC tubing, the tensile strength of the PVC/ABS/ α-SAN tubing obtained by the present invention, elongation at break and shock resistance all increase, and meet QB/T2480 index, can be widely used in pipeline material required in building.

Claims (1)

1. a high-impact PVC/ABS/ α-SAN tubing, is characterized in that, it is expected by A and B expects that equal proportion mixes extruding pelletization and is prepared from, and described A material, B material are obtained by the raw material extruding pelletization of following weight part respectively:
A expects:
Polyvinyl chloride SG-5 50-60, polyvinyl chloride reworked material 40-50, Calcium of intensifiens 20-30, chlorinatedpolyethylene 10-20, ABS high glue powder 5-10, dimethyl dimercapto 2-ethyl hexyl ethanoate tin 2-5, diisopropyl azodiformate 0.2-0.4, impact modifier ACR 5-10, vinyltriethoxysilane 0.3-0.5, oxidation inhibitor 1035 0.4-0.6, pentanoic 0.2-0.4, ethylene bis stearamide 0.3-0.5, two ten four carbon alcohols ester 0.1-0.2, modified Nano powder 5-10
Described modified Nano powder is obtained by following method: after calcium carbonate, celestite powder, the mixing of limestone powder equal proportion, scaling loss 4-5 hour at 600-700 DEG C, then nanometer powder is ground to form, admix the Di(dioctylpyrophosphato) ethylene titanate agitating being equivalent to powder weight 3-5% even, dry, be ground into powder;
B expects:
Polyvinyl chloride SG-5 50-60, ABS resin 20-30, α-SAN resin 20-30, poly-4-methyl-1-pentene 10-15, ACM 4-8, Cellmic C 121 2-5, chlorinatedpolyethylene 10-20, tetra isopropyl two (dioctyl phosphito acyloxy) titanic acid ester 0.3-0.5, two octadecanol ester 0.1-0.3, antioxidant 618 0.2-0.5, oxidized polyethlene wax 0.3-0.5, Zinic stearas 2-5, clorafin 1-3, modified coal ash 5-10
Described modified coal ash is made up of following method: the flyash after calcination is successively placed in 20-25% sulfuric acid, 16-24% sodium hydroxide solution successively, stir 20-22h, then the flyash leached from soda acid immersion liquid, with deionized water rinsing to neutral, and determined with the test of PH test paper, finally filter, dry, then flyash is pressed: wollastonite powder: three kinds of materials are sent into 1050-1100 DEG C of roasting 1-1.5 hour in fluidized-bed by ground dolomite weight ratio 1:0.3-0.5:0.5-0.8, grind to form nanometer powder after cooling;
The preparation method of described high-impact PVC/ABS/ α-SAN tubing, comprises the following steps:
The first step: prepare A material, B material respectively
The preparation of A material
(1) take each formula material by formula rate, the starting material weighed up are dropped into high-speed stirring 10-15 min in high-speed mixer, and temperature is 80-90 DEG C, after its moisture content fully evaporates, through cold mixer, material is down to 40-50 DEG C;
(2) above-mentioned compound is joined in parallel double-screw extruder carry out melt blending and granulation namely obtain A material, extruder barrel temperature is 245-255 DEG C, and die head temperature is 252-268 DEG C, and screw speed is 300-550rpm;
Two, the preparation of B material
The preparation of B material adopts the identical technique with A material to carry out granulation;
Second step: A expects to expect mixing granulation with B
Above-mentioned obtained A expected and B material equal proportion joins in parallel double-screw extruder and carries out melt blending and namely granulation obtains stuff and other stuff, extruder barrel temperature is 265-275 DEG C, and die head temperature is 272-286 DEG C, and screw speed is 300-550rpm;
3rd step: extrusion moulding
Adopt conical double screw extruder by the stuff and other stuff extrusion moulding of gained, obtain high-impact PVC/ABS/ α-SAN tubing, extruder barrel temperature is 276-298 DEG C, and die head temperature is 282-305 DEG C;
4th step: aftertreatment
The high-impact PVC/ABS/ α-SAN tubing of gained is cooled to 5-10 DEG C of sizings, then the tubing of sizing is cut by necessary requirement, finally the product of well cutting is packed, put into warehouse as ready.
CN201210357247.XA 2012-09-24 2012-09-24 High-impact PVC (polyvinyl chloride)/ABS (poly(acrylonitrile butadiene styrene))/alpha-SAN(alpha-styrene acrylonitrile copolymer) tubing and preparation method thereof Active CN102911451B (en)

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CN1210345C (en) * 2003-03-18 2005-07-13 四川大学 Polyvinyl chloride reinforcing and tougheness improving modifier and preparation and application thereof
CN1272377C (en) * 2004-11-15 2006-08-30 四川大学 Polyvinyl chloride plasticizing enhanced agglomerate and its preparation method and use
CN100556952C (en) * 2006-11-27 2009-11-04 天津德昊超微新材料有限公司 The PVC/ micro-nano composite powder and its preparation method
CN101693778B (en) * 2009-10-13 2012-02-08 广东联塑科技实业有限公司 PVC/ABS blend and pipe thereof
CN102134360B (en) * 2011-05-10 2012-06-06 上海远洲管业有限公司 Preparation method of super-strong high temperature-resistant chlorinated polyvinyl chloride tubes
CN102766302A (en) * 2012-08-13 2012-11-07 青岛海洋鲨科技有限公司 Formula for plastic pipe acrylonitrile butadiene styrene (ABS) modified hard chlorinated polyvinyl chloride and pipe preparation method

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