CN108659421A - Chliorinated polyvinyl chloride composition and tubing preparation method - Google Patents
Chliorinated polyvinyl chloride composition and tubing preparation method Download PDFInfo
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- CN108659421A CN108659421A CN201710207156.0A CN201710207156A CN108659421A CN 108659421 A CN108659421 A CN 108659421A CN 201710207156 A CN201710207156 A CN 201710207156A CN 108659421 A CN108659421 A CN 108659421A
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- polyvinyl chloride
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- antioxidant
- chloride composition
- chliorinated polyvinyl
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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
- C08L27/22—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 modified by chemical after-treatment
- C08L27/24—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 modified by chemical after-treatment halogenated
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
Abstract
Chliorinated polyvinyl chloride composition and tubing preparation method, belong to the field of polymers.It is characterized in that, parts by weight group becomes：100 parts of CPVC resins；1.5 ~ 2.0 parts of stabilizer；5 ~ 6 parts of impact modifier；2 ~ 3 parts of processing aid；1.5 ~ 2.0 parts of lubricant；1.5 ~ 2.0 parts of antioxidant；1.9 ~ 2.3 parts of colorant；1 ~ 5 part of filler；CPVC resins, which are that substance law polyvinyl chloride resin is chlorination modified, to be obtained, and impact modifier is the MBS resins of specific composition, and antioxidant is the composite antioxidant system of high-melting-point hindered phenol antioxygen and phosphite antioxidant.Preparation method is at 100 DEG C ~ 120 DEG C by material mixed on low speed；And by pellet extruding pipe material.The present composition improves the stability and heat resistance of material, from prepared by chlorinated polyvinyl chloride tubes there is good heat resistance and thermal stability, and it is easily processed into type.
Description
Technical field
Chliorinated polyvinyl chloride composition and tubing preparation method, belong to the field of polymers.
Background technology
Chliorinated polyvinyl chloride（CPVC）It is polyvinyl chloride（PVC）Product after chlorination, mass fraction containing chlorine element is 65%-
71% or so, physical property, mechanical property, especially heat resistance, solvent resistance, anti-flammability etc. have by a relatively large margin than PVC
It improves, wherein 30 DEG C -40 DEG C of vicat softening temperature ratio PVC high.CPVC be widely used in manufacturing various tubing, plank, proximate matter,
Moulding, foamed material, anticorrosive paint etc. have larger market prospects.
Since chlorinity increases, CPVC molecular defect structures increase, and thermal stability is deteriorated, while intermolecular interaction
Increase, melt viscosity is high when processing, poor fluidity.For CPVC tubing, the approach one for improving tubing heat resistance is to improve
The content of Cl element of content of Cl element in CPVC resins, usual CPVC resins increases by 1 percentage point, the dimension card softening temperature of tubing
Degree about improves 2 DEG C, and when resin content of Cl element is higher than 68%, thermal stability will drastically decline, while when processing tubing
Extruder back pressure steeply rises；Approach is second is that reduce the dosage of liquid adjuvants in formula system.This two methods is improving CPVC
While tubing heat resistance, difficulty of processing is also increased.
Invention content
The technical problem to be solved by the present invention is to：It overcomes the deficiencies of the prior art and provide a kind of with good heat resistance
And thermal stability, chliorinated polyvinyl chloride composition easily processed into type and tubing preparation method.
The technical solution adopted by the present invention to solve the technical problems is：The chliorinated polyvinyl chloride composition, feature exist
In parts by weight composition includes：100 parts of CPVC resins；1.5 ~ 2.0 parts of organic tin stabilizer；5 ~ 6 parts of impact modifier；Processing helps
2 ~ 3 parts of agent；1.5 ~ 2.0 parts of lubricant；1.5 ~ 2.0 parts of antioxidant；1.9 ~ 2.3 parts of colorant；1 ~ 5 part of filler；Described
CPVC resins are that substance law polyvinyl chloride resin is made by chlorination modified, and the average degree of polymerization of polyvinyl chloride resin is 1000, CPVC obtained
Resin chlorine element mass fraction accounts for 66% ~ 68%；The antioxidant be account for mass percent 50% ~ 70% high-melting-point hindered phenol it is anti-
The composite antioxidant system of oxygen agent and the high-melting-point phosphite antioxidant for accounting for mass percent 30% ~ 50%, the anti-impact change
Property agent be emulsion polymerization the metacrylate-butadiene with nucleocapsid structure-polystyrene ternary graft copolymer, stratum nucleare
Mass fraction in butadiene-styrene polymer shared by butadiene is 10% ~ 15%, shell methyl methacrylate and methyl-prop
The mass ratio of olefin(e) acid butyl ester is 1.7 ~ 2.3：2.7~3.3.
The present invention provides a kind of chliorinated polyvinyl chloride composition that most suitable tubing uses, through the invention with average polymerization
Degree carries out the chlorination modified of specific chlorination amount for 1000 substance law polyvinyl chloride resin, and inventor has found that this CPVC resins can be with
The composite antioxidant of organic tin stabilizer, specific composition used in the present invention, the impact modifier of specific composition and structure proportion
Form good synergistic effect, to greatly improve the heat resistance of tubing and the stability of material, from prepared by chlorination
Polychloroethylene pipes have good heat resistance and thermal stability, and easily processed into type.In the formula of the present invention preferably
Organic tin stabilizer, the optimal stability of gained tubing best with the adaptability of the present invention.
The antioxidant is to account for the high-melting-point hindered phenol antioxygen of mass percent 56% ~ 63% and account for mass percent
The composite antioxidant system of 37% ~ 44% high-melting-point phosphite antioxidant.The present invention provides preferred composite antioxidant configuration
Ratio, gained antioxidant and the synergistic effect of impact modifier of the present invention and stabilizer are stronger, product heat resistance it is more preferable.
Preferably, the high-melting-point hindered phenol antioxygen is 1,3,5- trimethyls -2,4,6- tri-（3 ', 5 '-two tertiary fourths
Base -4 '-hydroxyl Bian）Benzene.
Preferably, the high-melting-point phosphite antioxidant is double（2,4- di-tert-butyl-phenyls）Two phosphorous of pentaerythrite
Acid esters.
Preferred high-melting-point hindered phenol antioxygen and phosphite antioxidant adapt to the present invention the most, according to ratio of the present invention
Example carries out the heat resistance and stability of raising tubing that can be by a larger margin when collocation uses.
Preferably, the organic tin stabilizer is dibutyl solid organic-tin stabilizer（T-234）.The present invention is more preferable
Stabilizer be dibutyl solid organic-tin stabilizer, form preferable synergy with antioxidant energy Enough of the invention specific,
Heat resistance and stability can preferably be improved.It is further preferred that the dibutyl solid organic-tin stabilizer is two
Dibutyl tin laurate.
Preferably, the mass fraction in the butadiene-styrene polymer shared by butadiene is 12% ~ 13.5%.
Preferably, the mass ratio of the methyl methacrylate and butyl methacrylate is 2：3.
The present invention provides a kind of impact modifier best with allocation adaptability of the invention, is uniformly dispersed, with the present invention's
Antioxidant synergy is best, keeps tubing easily processed into type, and the ability of anti-deformation of gained tubing, deformation recovery capability increases
By force.
The processing aid is acrylic acid esters co-polymer（ACR）, such as PA-20.
The lubricant be low molecular weight polyethylene wax, two kinds of microwax, oxidized polyethylene wax, amides compound
Or it is a variety of.
The colorant is titanium dioxide and carbon black.
The titanium dioxide is rutile type titanium white, and such as R-902, dosage is 2 in chlorinated polyvinyl chloride tubes formula
Mass parts.
The carbon black is carbon carbon black, and dosage is 0.2 mass parts in chlorinated polyvinyl chloride tubes formula.
The filler is calcium carbonate, preferably active nano-calcium carbonate.
Silane coupling agent activation process is passed through on the active nano-calcium carbonate surface.
A kind of tubing preparation method using above-mentioned chliorinated polyvinyl chloride composition, which is characterized in that preparation process is：
1）Material compounding process：It will be mixed in high low speed mixer group after weighing by weight ratio, until 100 DEG C of mixing temperature ~
Material is put into low speed mixer at 120 DEG C, goes out pellet when temperature of charge is cooled to 37 DEG C ~ 43 DEG C；
2）Tube extrusion moulding process：By pellet, extruding pipe material, extruder temperature are 170 DEG C ~ 200 on the twin screw extruder
DEG C, tubing is pipe finished through cooling, cutting, expanding, packaging.
Preferably, step 1）The mixing temperature is 110 DEG C.
Compared with prior art, beneficial to effect possessed by chliorinated polyvinyl chloride composition of the invention and tubing preparation method
Fruit is：The present invention includes three crucial technical characteristics：1）The compound dystectic antioxidant of one kind is provided in the present invention to match
It closes using proportioning, the heat resistance of tubing can be effectively improved（Vicat softening temperature）.2）The present invention gives the MBS of specific composition
Impact modifier can more effectively improve the heat resistance of tubing.3）Used stabilizer selects solid organic-tin, and liquid is avoided to help
Adverse effect of the agent to heat resistance.The chlorination modified CPVC resins of specific chlorination amount can be with organic tin stabilizer used, spy
Surely the impact modifier of the composite antioxidant, specific composition and the structure proportion that form forms good synergistic effect, mutually promotes
Obtain heat-resisting, easy processing the tubing chliorinated polyvinyl chloride composition of height of the present invention.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, but is not intended to limit the present invention.
。
In embodiment 1-5, the chlorinity of CPVC is 67%.
The stratum nucleare butadiene-styrene polymer of impact modifier MBS, wherein butadiene content are in embodiment 1
12.5%, the mass ratio of shell methyl methacrylate and butyl methacrylate is 2：3；Impact modifier in embodiment 2,3
The stratum nucleare butadiene-styrene polymer of MBS, wherein butadiene content are 12%, shell methyl methacrylate and metering system
The mass ratio of acid butyl ester is 1.7：3.3；The stratum nucleare butadiene-styrene polymer of impact modifier MBS in embodiment 4,5,
Middle butadiene content is 13.5%, and the mass ratio of shell methyl methacrylate and butyl methacrylate is 2.3：2.7.
56% ~ 63% high-melting-point hindered phenol antioxygen
Composite antioxidant system hindered phenol antioxygen 330 accounts for 60% in embodiment 1, and phosphite antioxidant PEP-36A accounts for 40%, in fact
It applies composite antioxidant system hindered phenol antioxygen 330 in example 2,3 and accounts for 56%, phosphite antioxidant PEP-36A accounts for 44%, embodiment
4, composite antioxidant system hindered phenol antioxygen 330 accounts for 63% in 5, and phosphite antioxidant PEP-36A accounts for 37%.
。
In embodiment 6-10, the chlorinity of CPVC is 66%；The stratum nucleare butadiene-styrene of impact modifier MBS polymerize
Object, wherein butadiene content are 15%, and the mass ratio of shell methyl methacrylate and butyl methacrylate is 2：3；It is compound anti-
Oxygen agent system hindered phenol antioxygen 330 accounts for 50%, and phosphite antioxidant PEP-36A accounts for 50%.
。
In embodiment 11-15, the chlorinity of CPVC is 68%.The stratum nucleare butadiene-styrene of impact modifier MBS is poly-
Object is closed, wherein butadiene content is 10%, and the mass ratio of shell methyl methacrylate and butyl methacrylate is 2：3.It is compound
Antioxidant systems hindered phenol antioxygen 330 accounts for 70%, and phosphite antioxidant PEP-36A accounts for 30%.
。
In comparative example 1 ~ 5
CPVC resin chlorine element mass contents wherein used in comparative example 1 are 70%, remaining component is the same as embodiment 1.
Stabilizer used in comparative example 2 is liquid organic tin stabilizer TM-181FS, remaining component is the same as embodiment 1.
Impact modifier used in comparative example 3 is common MBS resins, remaining component is the same as embodiment 1.
Antioxidant used in comparative example 4 is hindered phenol antioxygen 300, remaining component is the same as embodiment 1.
Antioxidant used in comparative example 5 is phosphite antioxidant PEP-36A, remaining component is the same as embodiment 1.
The tubing pilot production of embodiment and comparative example：
（1）Raw material is compounded：Material is weighed up by raw material proportioning, is then added to high-speed mixer mixing, until 110 DEG C of mixing temperature,
Material is put into low speed mixer, is discharged when temperature of charge is cooled to 40 DEG C or so.
（2）Tube extrusion moulding process：By PP Pipe Compound, extruding pipe material, technological parameter are arranged such as on the twin screw extruder
Under：
Extruder temperature（℃）：1st area, 2nd area, 3rd area, 4 1st area of merging core head of area, 2nd area
190 185 180 175 170 190 200
According to city-building professional standard 18993.2-2003《Hot and cold water chliorinated polyvinyl chloride（PVC-C）Pipe-line system the 2nd
Part：Tubing》Detection performance, embodiment and comparative example result are as follows：
。
。
。
。
Comparative example 1 improves vicat softening temperature by improving the content of Cl element of CPVC resins, but causes molten when extrusion
Body pressure increases more（About 40%）, processing difficulties.Comparative example 2 uses common liquid organic tin stabilizer, directly reduces pipe
The vicat softening temperature of material.Comparative example 3 uses common MBS resin impact modifiers, the dimension card that not can effectively improve tubing soft
Change temperature.Comparative example 4 is used alone with comparative example 5, to the effect of raising tubing vicat softening temperature when not being used in combination.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, according to the technical essence of the invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. chliorinated polyvinyl chloride composition, which is characterized in that parts by weight, which form, includes：100 parts of CPVC resins；Organic tin stabilizer
1.5 ~ 2.0 parts；5 ~ 6 parts of impact modifier；2 ~ 3 parts of processing aid；1.5 ~ 2.0 parts of lubricant；1.5 ~ 2.0 parts of antioxidant；It
1.9 ~ 2.3 parts of toner；1 ~ 5 part of filler；The CPVC resins are that substance law polyvinyl chloride resin is made by chlorination modified, polyvinyl chloride resin
Average degree of polymerization be 1000, CPVC resins chlorine element mass fraction obtained accounts for 66% ~ 68%；The antioxidant is to account for quality
The high-melting-point hindered phenol antioxygen of percentage 50% ~ 70% and the high-melting-point phosphite antioxidant for accounting for mass percent 30% ~ 50%
Composite antioxidant system, the impact modifier be emulsion polymerization methacrylate-fourth two with nucleocapsid structure
Alkene-polystyrene ternary graft copolymer, the mass fraction in stratum nucleare butadiene-styrene polymer shared by butadiene is 10% ~
15%, the mass ratio of shell methyl methacrylate and butyl methacrylate is 1.7 ~ 2.3：2.7~3.3.
2. chliorinated polyvinyl chloride composition according to claim 1, it is characterised in that：The antioxidant is to account for quality hundred
Divide the high-melting-point hindered phenol antioxygen than 56% ~ 63% and accounts for the high-melting-point phosphite antioxidant of mass percent 37% ~ 44%
Composite antioxidant system.
3. chliorinated polyvinyl chloride composition according to claim 1 or 2, it is characterised in that：The high-melting-point hindered phenol
Antioxidant is 1,3,5- trimethyls -2,4,6- three（3 ', 5 '-di-t-butyls -4 '-hydroxyl Bian）Benzene.
4. chliorinated polyvinyl chloride composition according to claim 1 or 2, it is characterised in that：The high-melting-point phosphorous acid
Ester antioxidant is double（2,4- di-tert-butyl-phenyls）Pentaerythritol diphosphites.
5. chliorinated polyvinyl chloride composition according to claim 1, it is characterised in that：The organic tin stabilizer is two
Butyl solid organic-tin stabilizer.
6. chliorinated polyvinyl chloride composition according to claim 5, it is characterised in that：The dibutyl solid organic-tin
Stabilizer is dibutyl tin laurate.
7. chliorinated polyvinyl chloride composition according to claim 1, it is characterised in that：The butadiene-styrene is poly-
It is 12% ~ 13.5% to close the mass fraction in object shared by butadiene.
8. chliorinated polyvinyl chloride composition according to claim 1, it is characterised in that：The methyl methacrylate and first
The mass ratio of base butyl acrylate is 2：3.
9. a kind of tubing preparation method using claim 1 ~ 8 any one of them chliorinated polyvinyl chloride composition, feature
It is, preparation process is：
1）Material compounding process：It will be mixed in high low speed mixer group after weighing by weight ratio, until 100 DEG C of mixing temperature ~
Material is put into low speed mixer at 120 DEG C, goes out pellet when temperature of charge is cooled to 37 DEG C ~ 43 DEG C；
2）Tube extrusion moulding process：By pellet, extruding pipe material, extruder temperature are 170 DEG C ~ 200 on the twin screw extruder
DEG C, tubing is pipe finished through cooling, cutting, expanding, packaging.
10. the tubing preparation method of chliorinated polyvinyl chloride composition according to claim 9, it is characterised in that：Step 1）
The mixing temperature is 110 DEG C.
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| CN201710207156.0A CN108659421B (en) | 2017-03-31 | 2017-03-31 | Chlorinated polyvinyl chloride composition and pipe preparation method |
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| CN201710207156.0A CN108659421B (en) | 2017-03-31 | 2017-03-31 | Chlorinated polyvinyl chloride composition and pipe preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535618A (en) * | 2018-11-13 | 2019-03-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of high stability CPVC tubing and its mixing method |
| CN111944080A (en) * | 2020-07-15 | 2020-11-17 | 任丘市华凯通信设备有限公司 | CPVC (chlorinated polyvinyl chloride) pipe and preparation method thereof |
| CN113652045A (en) * | 2021-09-08 | 2021-11-16 | 无锡洪汇新材料科技股份有限公司 | High-impact-resistance CPVC (chlorinated polyvinyl chloride) injection molding pipe fitting and preparation method thereof |
| CN113736197A (en) * | 2021-08-18 | 2021-12-03 | 无锡洪汇新材料科技股份有限公司 | CPVC fire hose and preparation method thereof |
| CN115028946A (en) * | 2022-05-12 | 2022-09-09 | 贵州国塑科技管业有限责任公司 | CPVC (chlorinated polyvinyl chloride) pipe for high-pollution-resistant high-temperature organic wastewater and preparation method thereof |
| CN115584096A (en) * | 2021-07-06 | 2023-01-10 | 中国石油化工股份有限公司 | Chlorinated polyvinyl chloride composition and preparation method and application thereof |
| CN115772305A (en) * | 2022-12-03 | 2023-03-10 | 金川集团股份有限公司 | Preparation method of CPVC cold and hot water pipe |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535618A (en) * | 2018-11-13 | 2019-03-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of high stability CPVC tubing and its mixing method |
| CN111944080A (en) * | 2020-07-15 | 2020-11-17 | 任丘市华凯通信设备有限公司 | CPVC (chlorinated polyvinyl chloride) pipe and preparation method thereof |
| CN115584096A (en) * | 2021-07-06 | 2023-01-10 | 中国石油化工股份有限公司 | Chlorinated polyvinyl chloride composition and preparation method and application thereof |
| CN115584096B (en) * | 2021-07-06 | 2023-12-29 | 中国石油化工股份有限公司 | Chlorinated polyvinyl chloride composition and preparation method and application thereof |
| CN113736197A (en) * | 2021-08-18 | 2021-12-03 | 无锡洪汇新材料科技股份有限公司 | CPVC fire hose and preparation method thereof |
| CN113652045A (en) * | 2021-09-08 | 2021-11-16 | 无锡洪汇新材料科技股份有限公司 | High-impact-resistance CPVC (chlorinated polyvinyl chloride) injection molding pipe fitting and preparation method thereof |
| CN115028946A (en) * | 2022-05-12 | 2022-09-09 | 贵州国塑科技管业有限责任公司 | CPVC (chlorinated polyvinyl chloride) pipe for high-pollution-resistant high-temperature organic wastewater and preparation method thereof |
| CN115772305A (en) * | 2022-12-03 | 2023-03-10 | 金川集团股份有限公司 | Preparation method of CPVC cold and hot water pipe |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108659421B (en) | 2021-04-13 |
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