CN106398024A - High-rise laminated rainwater tubing and production method thereof - Google Patents

High-rise laminated rainwater tubing and production method thereof Download PDF

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CN106398024A
CN106398024A CN201610781435.3A CN201610781435A CN106398024A CN 106398024 A CN106398024 A CN 106398024A CN 201610781435 A CN201610781435 A CN 201610781435A CN 106398024 A CN106398024 A CN 106398024A
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preparation
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acr
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CN106398024B (en
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沈宇龙
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HUZHOU JINJIE INDUSTRY CO., LTD.
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Anhui Jin Jie Plastic Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B29L2023/22—Tubes or pipes, i.e. rigid
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
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    • 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
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

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Abstract

The invention belongs to the technical field of plastic tubing, and more specifically relates to high-rise laminated rainwater tubing and a production method thereof. The tubing comprises the following components: pvc resins, a stabilizing agent, stearic acid, modified ACR, titanium dioxide, and modified nanometer calcium carbonate; preparation of modified ACR comprises the following steps: (1) preparation of a seed emulsion: butyl acrylate and styrene are used as monomers, the emulsifier sodium dodecyl sulfate is added, an initiator potassium persulphate is added, and stirring and heating are carried out in order to prepare the seed emulsion; (2) preparation of a core: the potassium persulphate initiator, and butyl acrylate and styrene monomers are added continuously, tetrafluoroethene gas is introduced, and the core is obtained by preparation; (3) preparation of a housing: the sodium dodecyl sulfate emulsifier is added continuously, the potassium persulphate initiator is added, methyl methacrylate is added, modified nanometer SiO2 is added, and the housing is prepared; (4) spray drying is carried out in order to prepare modified ACR. The vinyl chloride tube has the advantages of good shock resistance and good pressure resistance.

Description

High-rise lamination rainwater tubing and preparation method thereof
Technical field
The invention belongs to plastic pipe technical field is and in particular to a kind of high level is laminated rainwater tubing and preparation method thereof.
Background technology
In water system, the features such as plastic pipe has that burn into sanitation performance is not good, is easily installed, obtain in China Widely popularize, substituting traditional galvanized iron conduit has been trend of the times.Plastic water pipe divides main inclusion by material：PVC, poly- Ethylene（PE）, polypropylene（PP）Deng because PVC pipeline is had compared with other polyolefin pipes, intensity is high, fire resistance is good, high The advantages of ring stiffness, excellent weather resistance, price are relatively low, is widely used.
But have that heat stability is poor, resistance to low temperature is poor in itself due to polyvinyl chloride resin, poor fluidity and toughness deficiency etc. lack Point, so various auxiliary agents will be added to improve its performance.Therefore, domestic, abroad in succession have developed high impact PVC pipe, Mainly carried out toughness reinforcing using elastomer, what application was most is chlorinated polyethylene（CPE）, PVC can be improved using the method Toughness, but the addition of CPE is larger, due to the netted toughening mechanism of CPE, harsher to fabrication process condition, and relatively Difficulty realizes rigidity-toughness balanced.Although, this tubing has obtained certain popularization, and it is at low temperature（-10℃）Impact resistance Can be still poor, existing Pipes Density is high simultaneously, and pressure-resistant time is short, produces Chen Bengao.Accordingly, it would be desirable to using preferably modification side Method improves the toughness of tubing, to meet its application in water-feeding pipes.
Content of the invention
An object of the present invention is to provide the high-rise lamination rainwater tubing that a kind of shock resistance is good, resistance to pressure is good.
The second object of the present invention is to provide the preparation side of the high-rise lamination rainwater tubing that shock resistance is good, resistance to pressure is good Method.
One of above-mentioned technical purpose of the present invention is achieved through the following technical solutions：
A kind of high-rise lamination rainwater tubing, in parts by weight, it consists of the following composition：
80～90 parts of Corvic；
1～10 part of stabilizer；
1～5 part of stearic acid；
1～10 part of modified ACR；
Titanium dioxide 2-8 part；
2～10 parts of modified nano calcium carbonate；
The preparation of described modification ACR comprises the following steps：
（1）The preparation of seed emulsion：In the reactor, using butyl acrylate, styrene as monomer, add emulsifying agent dodecane Base sodium sulfate, initiator potassium persulfate, stirring, intensification preparation seed emulsion；
（2）The preparation of kernel：On the basis of seed emulsion, continuously add potassium peroxydisulfate initiator, butyl acrylate, styrene Monomer, simultaneously under the conditions of 50～80 DEG C, is passed through tetrafluoroethylene gas in reactor bottom is to reactor, and keeps the pressure to be 0.3～0.8Mpa, reaction is lowered the temperature afterwards prepare kernel completely；
（3）The preparation of shell：In the later stage of kernel preparation reaction, add sodium lauryl sulphate emulsifying agent, potassium peroxydisulfate causes Agent, stirring, heats up, adds methyl methacrylate, add modified Nano SiO2Make organic monomer and Nano-meter SiO_22Mix homogeneously After carry out reaction and prepare shell；
（4）Reaction is completely spray-dried, and modification ACR is obtained.
The present invention high-rise lamination rainwater tubing is polychloroethylene pipes, and the present invention adds modified ACR in polyvinyl chloride pipe, Modified ACR is sufficiently stable core-shell structure polymer that esters of acrylic acid is formed through chemical graft.In the modified ACR of preparation During by introduce tetrafluoroethylene monomer, there is in tetrafluoroethylene monomer the very strong fluorine atom of polarity, change stratum nucleare point Minor structure, increasing the heat stability of stratum nucleare, reducing the surface energy of stratum nucleare, imparting the good low-temperature impact resistance of ACR and resistance to Hou Xing.With BA-St as core in the preparation process of modified ACR, with methyl methacrylate as shell, styrene Addition can adjust the vitrification point of copolymer, reduce film-forming temperature so that the nucleocapsid structure particle diameter of synthesis compares Little, also ratio is more uniform for particle diameter distribution, and stability is preferable.Methyl methacrylate can keep stratum nucleare size as shell one side Stability and give inner elastomeric core certain hardness, the dissolubility of another aspect methyl methacrylate and Corvic Parameter similar, can improve the compatibility of modified ACR and matrix.It is grafted inorganic nano outside methyl methacrylate shell layer simultaneously SiO2, inorganic nano SiO2Addition further increase toughness and the intensity of material.
Preferably, described stabilizer is one of organic tin stabilizer, Pb stabilizer, calcium zinc stabilizer or several Kind.
Preferably, the preparation process of described modification ACR（1）The preparation of middle seed emulsion, wherein each raw material is divided by quality Number meter, consisting of：
10～20 parts of butyl acrylate；
5～15 parts of styrene；
0.5～5 part of sodium lauryl sulphate；
0.1～0.8 part of potassium peroxydisulfate.
Preferably, the preparation process of described modification ACR（2）The preparation of middle kernel, wherein each raw material in parts by weight, Consisting of：
40～60 parts of butyl acrylate；
15～25 parts of styrene；
5～10 parts of tetrafluoroethene；
0.05～0.3 part of potassium peroxydisulfate.
Preferably, the preparation process of described modification ACR（3）The preparation of middle shell, wherein each raw material in parts by weight, Consisting of：
0.1～0.8 part of potassium peroxydisulfate；
15～25 parts of methyl methacrylate；
0.5～1 part of sodium lauryl sulphate；
Modified Nano SiO22～8 parts.
Preferably, described modified Nano SiO2Preparation method be：By 80～100 parts of Nano-meter SiO_22Add ethanol water-soluble In liquid, and make it fully dispersed under strong stirring；Add 5～10 parts of organo silane coupling agents in dispersion liquid, in temperature be After magnetic agitation is reacted 5～8 hours at 50～70 DEG C, it is cooled to room temperature sucking filtration, drying, grinding obtain modified Nano SiO2.
Nano-meter SiO_22Big for a kind of inorganic material, its specific surface energy, it is difficult to dispersion in organic family macromolecule, by receiving Rice SiO2Surface modification is so that Nano-meter SiO_22Surface grafting organo silane coupling agent is it is easier to disperse in Organic substance.
Preferably, described silane coupled modifying agent is VTES, vinyltrimethoxy silane, second One of thiazolinyl three (2- methoxy ethoxy) silane.
Preferably, the preparation method of described modified nano calcium carbonate is：Nano-calcium carbonate powder body and decontamination water are existed Stir in ball mill；Then carboxy terminatedpolybutadiene or Carboxy polymer are added ball milling in ball mill to obtain slurry； By slurry through filter pressing, drying, you can prepared modified calcium carbonate.
Nano-calcium carbonate surface, uniformly coats one layer of carboxyl polymer, thus improve nano-calcium carbonate nonpolar molten Dispersibility in agent.Modified nano-calcium carbonate has good dispersibility and brilliant looks form, as the feature of polymer Packing material has good dispersive property, and processing characteristics, and can improve the physicochemical property of product.
Preferably, described carboxy terminatedpolybutadiene or Carboxy polymer are 1～1.5 with the mass ratio of nano-calcium carbonate ：10～15.
The two of the above-mentioned technical purpose of the present invention are achieved through the following technical solutions：
A kind of preparation method of high-rise lamination rainwater tubing, comprises the following steps：
（1）Start batch mixer to sequentially add described raw material in proportion, temperature is risen to after 100 DEG C～130 DEG C, then starts cold Mixed, after temperature is down to 30 DEG C～50 DEG C, material is released；
（2）By step（1）Extruder put into by material after middle cooling, and material extrudes embryonic tube through mould mouth；The machine of described extruder Cylinder includes four heating regions, and the temperature in each region is：
One area：160 DEG C～175 DEG C,
2nd area：158 DEG C～170 DEG C,
3rd area：155 DEG C～165 DEG C,
4th area：155 DEG C～160 DEG C；
Described mould includes four heating regions, and the temperature in each region is：
One area：165 DEG C～170 DEG C,
2nd area：165 DEG C～175 DEG C,
3rd area：170 DEG C～180 DEG C,
4th area：180 DEG C～210 DEG C.
（3）Embryonic tube forms polychloroethylene pipes through Vacuum shaping cooler bin cooling and shaping and traction molding；
（4）Above-mentioned polychloroethylene pipes finished product after twining membrane coiler packaging, cutting.
The polychloroethylene pipes of the present invention, in traditional formulating of recipe for pipes, employ ACR as processing aid, can be obvious Shorten fusion time, extruded product can be made its counter balance torque improve so as to plasticizing is uniform；Improve its tensile property, meanwhile, plus Enter ACR and can overcome chill mark, reduce bubble；Add ACR can improve melt extensibility, overcome melt fracture phenomena, add multiple Closing stabilizer is to suppress polychloroethylene pipes product variable color, decomposition, performance depreciation in process, preparation technology letter Single, low cost, preparation efficiency is high, and prepared polychloroethylene pipes have that tensile property is good, and resistance to impact is good, is not susceptible to fragility Destroy.
In sum, the invention has the advantages that：
1. the present invention adds modified ACR in polyvinyl chloride pipe, and modified ACR is that esters of acrylic acid is formed through chemical graft Sufficiently stable core-shell structure polymer.By introducing tetrafluoroethylene gas, tetrafluoroethene gas during the modified ACR of preparation There is in body the very strong fluorine atom of polarity, changing the molecular structure of stratum nucleare, the heat stability of increase stratum nucleare is, reduce the table of stratum nucleare Face energy, imparts the good low-temperature impact resistance of ACR and weatherability.It is passed through tetrafluoroethylene gas in reactor bottom simultaneously On the one hand the gas being passed through can be stirred to material so that material mixes evenly；On the other hand it is passed through tetrafluoro from bottom Ethylene gas and material from top to bottom moves under gravity, both reverse movements are so that tetrafluoroethylene gas are to material Contact more abundant, treatment effect is more preferable.With BA-St as core in the preparation process of modified ACR, with methyl Acrylic acid methyl ester. is shell, cinnamic addition can adjust the vitrification point of copolymer, reduces film-forming temperature so that synthesis Nucleocapsid structure particle diameter is smaller, and also ratio is more uniform for particle diameter distribution, and stability is preferable.Methyl methacrylate is as shell one Aspect can keep the stability of stratum nucleare size and give inner elastomeric core certain hardness, another aspect methyl methacrylate with The solubility parameter of Corvic is close, can improve the compatibility of modified ACR and matrix.
2. in the Nano-meter SiO_2 of the shell coating modification of ACR2, inorganic nano SiO2Itself be there is to obtain skin effect and amount Sub- effect, not only can improve the toughness of ACR, can also improve rigidity and the intensity of material simultaneously.
3. add modified nano calcium carbonate in polyvinyl chloride pipe, in one layer of modified nano calcium carbonate coated with uniform Carboxyl polymer, thus improve the dispersibility in non-polar solven of nano-calcium carbonate.Modified nano-calcium carbonate has Good dispersibility and brilliant looks form, the functional filling material as polymer has good dispersive property, and processability Can, and the physicochemical property of product can be improved.
Specific embodiment
Embodiment 1
A kind of pressure draining polyvinyl chloride pipe, in parts by weight, it consists of the following composition：
80 parts of Corvic；
1 part of organic tin stabilizer；
1 part of stearic acid；
1 part of modified ACR；
2 parts of titanium dioxide；
2 parts of modified nano calcium carbonate；
Wherein organic tin stabilizer can be one of maleate, mercaptides, mercapto soap；Corvic SG-5 resin sent out by model ethylene；
In raw material, the preparation method of modified ACR is：
（1）The preparation of seed emulsion：In terms of mass fraction, add 10 parts of butyl acrylate, 5 parts of styrene conducts in the reactor Monomer, adds 0.5 part of sodium lauryl sulphate emulsifying agent, 0.1 part of potassium peroxydisulfate initiator, stirs, is warmed up to 40 DEG C～50 DEG C Prepare seed emulsion；
（2）The preparation of kernel：On the basis of above-mentioned seed emulsion, continuously add 0.05 part of potassium peroxydisulfate initiator, continue simultaneously Continuous addition 40 parts of butyl acrylate, 15 parts of styrene monomers are simultaneously under the conditions of 50 DEG C, logical in reactor bottom is to reactor Enter tetrafluoroethylene gas, and keep pressure to be 0.3Mpa, reaction is lowered the temperature afterwards prepare kernel completely；
（3）The preparation of shell：In the later stage of kernel preparation reaction, add 0.5 part of sodium lauryl sulphate emulsifying agent, 0.1 part of mistake Potassium sulfate initiator, stirring, it is warming up to 70 DEG C, add 15 parts of methyl methacrylates, and add 2 parts of modified Nano SiO2So that Organic monomer and Nano-meter SiO_22Carry out reaction after mix homogeneously and prepare shell；Wherein modified Nano SiO2Preparation method be：By 80 Part Nano-meter SiO_22Add in ethanol water, and make it fully dispersed under strong stirring；5 parts of vinyls are added in dispersion liquid Three (2- methoxy ethoxy) silane coupler, after magnetic agitation is reacted 5 hours at temperature is 50 DEG C, is cooled to room temperature simultaneously Sucking filtration, drying, grinding obtain modified Nano SiO2.
（4）By step（3）The product of middle preparation, spray-dried, modification ACR is obtained.
In raw material, the preparation method of modified nano calcium carbonate is：By nano-calcium carbonate powder body and decontamination water in ball mill Stir；Then carboxy terminatedpolybutadiene polymer is added ball milling in ball mill to obtain slurry；By slurry through filter pressing, drying, Can be prepared by modified calcium carbonate.Wherein carboxy terminatedpolybutadiene and the mass ratio of nano-calcium carbonate are 1：10.
The preparation method of above-mentioned high-rise lamination rainwater tubing is：（1）Start batch mixer to add above raw material in proportion successively Enter, temperature is risen to after 100 DEG C, start cold mixed, after temperature is down to 30 DEG C, material is released；
（2）By step（1）Extruder put into by material after middle cooling, and material extrudes embryonic tube through mould mouth；The machine barrel of extruder Barrel zone temperature is set to 160 DEG C, 158 DEG C, 155 DEG C, 155 DEG C, and the temperature setting of mould bag is：
165℃、165℃、170℃、180℃；
（3）Embryonic tube forms polychloroethylene pipes through Vacuum shaping cooler bin cooling and shaping and traction molding；
（4）Above-mentioned polychloroethylene pipes finished product after twining membrane coiler packaging, cutting.
Embodiment 2
A kind of high-rise lamination rainwater tubing, in parts by weight, it consists of the following composition：
85 parts of Corvic；
5 parts of Pb stabilizer；
3 parts of stearic acid；
5 parts of modified ACR；
5 parts of titanium dioxide；
6 parts of modified nano calcium carbonate；
Wherein organic tin stabilizer can be one of lead sulfate tribasic, dibasic lead phosphite, hard lead acid；
In raw material, the preparation method of modified ACR is：
（1）The preparation of seed emulsion：In terms of mass fraction, in the reactor, 15 parts of butyl acrylate, 10 parts of styrene are added to make For monomer, add 2.5 parts of sodium lauryl sulphate emulsifying agents, 0.5 part of potassium peroxydisulfate initiator, stir, be warmed up to 40 DEG C～50 DEG C prepare seed emulsion；
（2）The preparation of kernel：On the basis of above-mentioned seed emulsion, continuously add 0.15 part of potassium peroxydisulfate initiator, continue simultaneously Continuous addition 50 parts of butyl acrylate, 20 parts of styrene monomers are simultaneously under the conditions of 70 DEG C, logical in reactor bottom is to reactor Enter tetrafluoroethylene gas, and keep pressure to be 0.6Mpa, reaction is lowered the temperature afterwards prepare kernel completely；
（3）The preparation of shell：In the later stage of kernel preparation reaction, add 0.7 part of sodium lauryl sulphate emulsifying agent, 0.5 part of mistake Potassium sulfate initiator, stirring, it is warming up to 70 DEG C, add 20 parts of methyl methacrylates, and add 5 parts of modified Nano SiO2So that Organic monomer and Nano-meter SiO_22Carry out reaction after mix homogeneously and prepare shell；Wherein modified Nano SiO2Preparation method be：By 90 Part Nano-meter SiO_22Add in ethanol water, and make it fully dispersed under strong stirring；8 parts of vinyls are added in dispersion liquid Trimethoxysilane coupling agent, after at temperature is 60 DEG C, magnetic agitation is reacted 6 hours, be cooled to room temperature sucking filtration, drying, Grinding obtains modified Nano SiO2.
（4）By step（3）The product of middle preparation, spray-dried, modification ACR is obtained.
In raw material, the preparation method of modified nano calcium carbonate is：By nano-calcium carbonate powder body and decontamination water in ball mill Stir；Then Carboxy polymer is added ball milling in ball mill to obtain slurry；By slurry through filter pressing, drying, you can Prepared modified calcium carbonate.Wherein carboxy terminatedpolybutadiene and the mass ratio of nano-calcium carbonate are 1.2：13.
The preparation method of above-mentioned high-rise lamination rainwater tubing is：（1）Start batch mixer to add above raw material in proportion successively Enter, temperature is risen to after 115 DEG C, start cold mixed, after temperature is down to 40 DEG C, material is released；
（2）By step（1）Extruder put into by material after middle cooling, and material extrudes embryonic tube through mould mouth；The machine barrel of extruder Barrel zone temperature is set to 168 DEG C, 165 DEG C, 160 DEG C, 158 DEG C, and the temperature setting of mould bag is：
168℃、170℃、175℃、190℃；
（3）Embryonic tube forms polychloroethylene pipes through Vacuum shaping cooler bin cooling and shaping and traction molding；
（4）Above-mentioned polychloroethylene pipes finished product after twining membrane coiler packaging, cutting.
Embodiment 3
A kind of high-rise lamination rainwater tubing, in parts by weight, it consists of the following composition：
90 parts of Corvic；
10 parts of calcium zinc stabilizer；
5 parts of stearic acid；
10 parts of modified ACR；
8 parts of titanium dioxide；
10 parts of modified nano calcium carbonate；
In raw material, the preparation method of modified ACR is：
（1）The preparation of seed emulsion：In terms of mass fraction, in the reactor, 20 parts of butyl acrylate, 15 parts of styrene are added to make For monomer, add 5 parts of sodium lauryl sulphate emulsifying agents, 0.8 part of potassium peroxydisulfate initiator, stir, be warmed up to 40 DEG C～50 DEG C Prepare seed emulsion；
（2）The preparation of kernel：On the basis of above-mentioned seed emulsion, continuously add 0.3 part of potassium peroxydisulfate initiator, continue simultaneously Add 60 parts of butyl acrylate, 25 parts of styrene monomers, simultaneously under the conditions of 80 DEG C, be passed through in reactor bottom is to reactor Tetrafluoroethylene gas, and keep pressure to be 0.8Mpa, reaction is lowered the temperature afterwards prepare kernel completely；
（3）The preparation of shell：In the later stage of kernel preparation reaction, add 1 part of sodium lauryl sulphate emulsifying agent, 0.8 part of over cure Sour potassium initiator, stirring, it is warming up to 70 DEG C, add 25 parts of methyl methacrylates, and add 8 parts of modified Nano SiO2So that having Machine monomer and Nano-meter SiO_22Carry out reaction after mix homogeneously and prepare shell；Wherein modified Nano SiO2Preparation method be：By 100 Part Nano-meter SiO_22Add in ethanol water, and make it fully dispersed under strong stirring；10 parts of ethylene are added in dispersion liquid Ethyl triethoxy silicane alkane coupling agent, after magnetic agitation is reacted 8 hours at temperature is 70 DEG C, is cooled to room temperature sucking filtration, baking Dry, grinding obtains modified Nano SiO2.
（4）By step（3）The product of middle preparation, spray-dried, modification ACR is obtained.
In raw material, the preparation method of modified nano calcium carbonate is：By nano-calcium carbonate powder body and decontamination water in ball mill Stir；Then Carboxy polymer is added ball milling in ball mill to obtain slurry；By slurry through filter pressing, drying, you can Prepared modified calcium carbonate.Wherein carboxy terminatedpolybutadiene and the mass ratio of nano-calcium carbonate are 1.5：15.
The preparation method of above-mentioned high-rise lamination rainwater tubing is：（1）Start batch mixer to add above raw material in proportion successively Enter, temperature is risen to after 130 DEG C, start cold mixed, after temperature is down to 50 DEG C, material is released；
（2）By step（1）Extruder put into by material after middle cooling, and material extrudes embryonic tube through mould mouth；The machine barrel of extruder Barrel zone temperature is set to 175 DEG C, 170 DEG C, 165 DEG C, 160 DEG C, and the temperature setting of mould bag is：
170℃、175℃、180℃、210℃；
（3）Embryonic tube forms polychloroethylene pipes through Vacuum shaping cooler bin cooling and shaping and traction molding；
（4）Above-mentioned polychloroethylene pipes finished product after twining membrane coiler packaging, cutting.
Comparative example 1
With embodiment 1, difference is to be added without being passed through tetrafluoroethylene gas during preparation ACR.
Comparative example 2
With embodiment 2, difference is to be added without modified Nano SiO during preparation ACR2.
Comparative example 3
With embodiment 3, difference is in raw material to be not added with modified nano calcium carbonate.
Comparative example 4
With embodiment 1, difference is to be passed through tetrafluoroethylene gas in reactor head during preparation ACR.
According to IS0179：2000 test example 1-3 and the shock resistance of polyvinyl chloride pipe that comparative example 1-3 obtains is strong Degree, tests the tensile yield strength of example 1-3 and comparative example 1-3, result is in shown in table 1 according to ASTM D638.From table 1 It can be seen that with the increase impact strength of modified ACR, tensile yield strength all with increase in embodiment 1-3.From to reality Apply example 1 and comparative example 4 as can be seen that the impact strength of comparative example 4 and tensile yield strength are respectively less than embodiment 1, this be by Material can be stirred so that material mixing in being passed through, from reactor head, the gas that tetrafluoroethylene gas one side is passed through Evenly；Another aspect is passed through tetrafluoroethylene gas from bottom and material from top to bottom moves under gravity, and both are inverse To motion so that tetrafluoroethylene gas are more abundant to the contact of material, treatment effect more preferably, improves the performance of product.From right Nano-meter SiO_2 is found out in ratio 1 and embodiment 1 contrast2Be added in greatly enhance polyvinyl chloride pipe impact strength, Tensile yield strength, Nano-meter SiO_22The methyl methacrylate shell layer of ACR is coated, inorganic nano SiO2Itself had Obtain skin effect and quantum effect, the toughness of ACR not only can be improved, rigidity and the intensity of material can also be improved simultaneously.
Table 1 experimental test result
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, and those skilled in the art exist As needed the present embodiment can be made after reading this specification does not have the modification of creative contribution, but as long as in the present invention Right in all protected by Patent Law.

Claims (10)

1. a kind of high-rise lamination rainwater tubing it is characterised in that：In parts by weight, it consists of the following composition：
80～90 parts of Corvic；
1～10 part of stabilizer；
1～5 part of stearic acid；
1～10 part of modified ACR；
2～8 parts of titanium dioxide；
2～10 parts of modified nano calcium carbonate；
The preparation of described modification ACR comprises the following steps：
（1）The preparation of seed emulsion：In the reactor, using butyl acrylate, styrene as monomer, add emulsifying agent dodecane Base sodium sulfate, initiator potassium persulfate, stirring, intensification preparation seed emulsion；
（2）The preparation of kernel：On the basis of seed emulsion, continuously add potassium peroxydisulfate initiator, butyl acrylate, styrene Monomer, simultaneously under the conditions of 50～80 DEG C, is passed through tetrafluoroethylene gas in reactor bottom is to reactor, and keeps the pressure to be 0.3～0.8Mpa, reaction is lowered the temperature afterwards prepare kernel completely；
（3）The preparation of shell：In the later stage of kernel preparation reaction, add sodium lauryl sulphate emulsifying agent, potassium peroxydisulfate causes Agent, stirring, heats up, adds methyl methacrylate, add modified Nano SiO2Make organic monomer and Nano-meter SiO_22Mix homogeneously After carry out reaction and prepare shell；
（4）Reaction is completely spray-dried, and modification ACR is obtained.
2. a kind of high-rise lamination rainwater tubing according to claim 1 it is characterised in that：Described stabilizer is that organotin is steady Determine one or more of agent, Pb stabilizer, calcium zinc stabilizer.
3. a kind of high-rise lamination rainwater tubing according to claim 1 it is characterised in that：The preparation step of described modification ACR Suddenly（1）The preparation of middle seed emulsion, wherein each raw material in parts by weight, consisting of：
10～20 parts of butyl acrylate；
5～15 parts of styrene；
0.5～5 part of sodium lauryl sulphate；
0.1～0.8 part of potassium peroxydisulfate.
4. a kind of high-rise lamination rainwater tubing according to claim 1 it is characterised in that：The preparation step of described modification ACR Suddenly（2）The preparation of middle kernel, wherein each raw material in parts by weight, consisting of：
40～60 parts of butyl acrylate；
15～25 parts of styrene；
5～10 parts of tetrafluoroethene；
0.05～0.3 part of potassium peroxydisulfate.
5. a kind of high-rise lamination rainwater tubing according to claim 1 it is characterised in that：The preparation step of described modification ACR Suddenly（3）The preparation of middle shell, wherein each raw material in parts by weight, consisting of：
0.1～0.8 part of potassium peroxydisulfate；
15～25 parts of methyl methacrylate；
0.5～1 part of sodium lauryl sulphate；
Modified Nano SiO22～8 parts.
6. a kind of high-rise lamination rainwater tubing according to claim 5 it is characterised in that：Described modified Nano SiO2System Preparation Method is：By 80～100 parts of Nano-meter SiO_22Add in ethanol water, and make it fully dispersed under strong stirring；Dividing 5～10 parts of organo silane coupling agents are added in dispersion liquid, after at temperature is 50～70 DEG C, magnetic agitation is reacted 5～8 hours, cold But to room temperature and sucking filtration, drying, grinding obtain modified Nano SiO2.
7. a kind of high-rise lamination rainwater tubing according to claim 6 it is characterised in that：Described silane coupled modifying agent is One of VTES, vinyltrimethoxy silane, vinyl three (2- methoxy ethoxy) silane.
8. a kind of high-rise lamination rainwater tubing according to claim 1 it is characterised in that：Described modified nano calcium carbonate Preparation method is：Nano-calcium carbonate powder body is stirred in ball mill with decontamination water；Then by carboxy terminatedpolybutadiene or Carboxy polymer adds ball milling in ball mill to obtain slurry；By slurry through filter pressing, drying, you can prepared modified calcium carbonate.
9. a kind of high-rise lamination rainwater tubing according to claim 8 it is characterised in that：Described carboxy terminatedpolybutadiene or carboxylic Base styrene-butadiene polymer is 1～1.5 with the mass ratio of nano-calcium carbonate：10～15.
10. according to a kind of arbitrary described preparation method of high-rise lamination rainwater tubing of claim 1-9 it is characterised in that：Bag Include following steps：
（1）Start batch mixer to sequentially add raw material in proportion, temperature risen to after 100 DEG C～130 DEG C, then start cold mixed, After temperature is down to 30 DEG C～50 DEG C, material is released；
（2）By step（1）Extruder put into by material after middle cooling, and material extrudes embryonic tube through mould mouth；The machine of described extruder Cylinder includes four heating regions, and the temperature in each region is：
One area：160 DEG C～175 DEG C,
2nd area：158 DEG C～170 DEG C,
3rd area：155 DEG C～165 DEG C,
4th area：155 DEG C～160 DEG C；
Described mould includes four heating regions, and the temperature in each region is：
One area：165 DEG C～170 DEG C,
2nd area：165 DEG C～175 DEG C,
3rd area：170 DEG C～180 DEG C,
4th area：180 DEG C～210 DEG C；
（3）Embryonic tube forms polychloroethylene pipes through Vacuum shaping cooler bin cooling and shaping and traction molding；
（4）Above-mentioned polychloroethylene pipes finished product after twining membrane coiler packaging, cutting.
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