CN106750988B - A kind of PPR pipe and preparation method thereof with excellent low temperature toughness - Google Patents
A kind of PPR pipe and preparation method thereof with excellent low temperature toughness Download PDFInfo
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- CN106750988B CN106750988B CN201611029459.XA CN201611029459A CN106750988B CN 106750988 B CN106750988 B CN 106750988B CN 201611029459 A CN201611029459 A CN 201611029459A CN 106750988 B CN106750988 B CN 106750988B
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- ppr pipe
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- temperature toughness
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
-
- 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
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
Abstract
The present invention relates to a kind of PPR pipe with excellent low temperature toughness, the PPR pipe is made of following raw material by mass fraction: 100 parts of atactic copolymerized polypropene；0.1~5 part of coupling agent；1~20 part of toughener；1~20 part of whisker loaded beta nucleating agent；0.1~3 part of antioxidant；0.1~5 part of color masterbatch.PPR pipe provided by the invention has excellent low-temperature flexibility, while having preferable rigidity, intensity and pressure-resistant performance；PPR pipe provided by the invention with excellent low temperature toughness improve tubing low temperature environment transport and application reliability.
Description
Technical field
The present invention relates to tubing technical fields, and in particular to a kind of PPR pipe and its preparation with excellent low temperature toughness
Method.
Background technique
Atactic copolymerized polypropene (PPR) tubing is that the third generation of the MODIFIED PP tubing of European early 1990s exploitation produces
Product.PPR is made, wherein the ethylene containing about 3% using atactic copolymerized polypropene as base-material after modified processing.PPR pipe is with stainless
It is erosion, non-leakage, non-scaling, not only heat-resisting but also pressure-resistant, can with building with the longevity many advantages, such as, be increasingly subject to the favor of people.But
It is that low temperature brittleness can occur for PPR pipe, at low ambient temperatures, PPR pipe is easily damaged during transportation, this greatly makes
About use of the PPR pipe in extremely frigid zones.
Elastomer has very high elasticity, and glass transition temperature is very low, can significantly improve the black brittleness of PPR.But simultaneously
Bring is declining to a great extent for PPR rigidity, intensity and heat distortion temperature.Inorganic rigid particle has reinforcing effect, can same bullet
Property body coordination plasticizing PPR, the tubing being prepared can also be kept while with preferable low-temperature flexibility it is original rigidity,
Intensity.But the compound system of elastomer, inorganic rigid particle and PPR is often difficult to obtain single, steadily phase, institute
PPR pipe obtained is then had too many difficulties to cope in terms of pressure resistance.
Beta-crystalline polyacrylic has the advantages that elasticity modulus and yield strength is low, impact strength and heat distortion temperature are high, Gao Han
Amount Beta-crystalline polyacrylic is the ideal style of polypropylene toughening, and addition beta nucleater is to obtain having for the generally acknowledged row of high-content beta crystal
The approach of effect.But from the point of view of practical situations, polyacrylic beta-crystalline form content is but unable to reach expection, the low temperature of PPR pipe
Toughness also cannot effectively improve.In conclusion being highly desirable to research and develop a kind of good low-temperature flexibility, rigidity and intensity
High, good pressure-resistant performance PPR pipe.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of PPR pipe with excellent low temperature toughness,
PPR pipe provided by the invention has excellent low-temperature flexibility, while having preferable rigidity, intensity and pressure-resistant performance.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of PPR pipe with excellent low temperature toughness, the PPR pipe are made of following raw material by mass fraction:
100 parts of atactic copolymerized polypropene；
0.1~5 part of coupling agent；
1~20 part of toughener；
1~20 part of whisker loaded beta nucleating agent；
0.1~3 part of antioxidant；
0.1~5 part of color masterbatch.
Whisker refers to the mono-crystlling fibre material with certain draw ratio and area, whisker atomic structural arrangement in crystallization
High-sequential, internal almost zero defect, therefore its intensity are close to valence bond theory intensity between material atom, considerably beyond mesh
The preceding reinforcing agent used.Whisker also has good compatibility, excellent flatness and chemical stability etc., and whisker can be
What is be distributed in macromolecule matrix is very uniform, has better reinforcing effect, is effectively improved toughener and β crystalline substance bring material modulus
Decline.
The present invention uses whisker loaded beta nucleating agent and toughener to enhance atactic copolymerized polypropene with coordination plasticizing.Whisker is negative
Carrying beta nucleater makes the nucleating agent in system be uniformly dispersed, and is conducive to improve β crystalline substance nucleation capability, so that beta crystal content is improved, into one
The low-temperature flexibility of raising system is walked, on the other hand, whisker loaded beta nucleating agent can also significantly improve the pressure-resistant performance of PPR pipe.
The stress that whisker improves elastomer generation concentrates on effective transmitting in matrix resin, is also easy to produce the plastic deformation consumption of large area
Many energy are dissipated, the effect of collaboration enhancing low-temperature flexibility is equally shown.In addition, whisker has excellent humidification,
Compensate for the decline of elastomer and β crystalline substance bring material modulus.Synergistic effect between toughener and whisker load nucleating agent is assigned
PPR pipe excellent low-temperature flexibility and mechanical property are given.
Preferably, the mass ratio of whisker and beta nucleater is 100:1~25 in the whisker loaded beta nucleating agent.It is more highly preferred to
Ground, the mass ratio of whisker and beta nucleater is 100:5~15 in the whisker loaded beta nucleating agent.
Preferably, the whisker loaded beta nucleating agent the preparation method comprises the following steps: first with surface treating agent handle whisker surface, so
Dispersion mixing in high-speed mixer, whisker loaded beta nucleating agent obtained by drying is added in treated whisker and beta nucleater afterwards.Institute
Stating surface treating agent can be coupling agent such as silane coupling agent.
Preferably, the whisker is calcium carbonate, aluminium borate, potassium titanate, magnesium sulfate, aluminium oxide, one in ZnOw
Kind is several.
Preferably, the beta nucleater is organic carboxyl acid salt and/or amides nucleating agent.It is further preferable that the β at
Core agent is calcium suberate, one or more of calcium pimelate, TMB-5.
Preferably, the toughener is ethylene-octene copolymer, ethylene-propylene-diene copolymer, styrene-fourth two
Alkene-polystyrene ternary segmented copolymer, hydrogenated styrene-butadiene-styrene ternary block polymer, styrene-isoamyl two
One of alkene-polystyrene ternary segmented copolymer, hydrogenated styrene isoprene-polystyrene ternary segmented copolymer are several
Kind.It is further preferable that the toughener is ethylene-octene copolymer.
Preferably, the coupling agent is silane coupling agent, in titanate coupling agent, aluminate coupling agent, rare-earth coupling agent
One or more.
Preferably, the antioxidant includes primary antioxidant and auxiliary antioxidant, and the primary antioxidant is hindered phenol or thioesters
One or more of kind antioxidant, the auxiliary antioxidant are phosphite ester antioxidant.Preferably, the primary antioxidant is
Four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters (antioxidant 1010), the auxiliary antioxygen
Agent is three [2,4- di-tert-butyl-phenyl] phosphite esters (irgasfos 168).
Compared with prior art, the invention has the following beneficial effects:
The present invention is prepared by the coordination plasticizing humidification of whisker loaded beta nucleating agent and toughener elastomer
PPR pipe has excellent low-temperature flexibility and mechanical property, maintains the rigidity, intensity and pressure-resistant performance of PPR, improves
PPR pipe low temperature environment transport and application reliability.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.These embodiments are retouched to typical case of the invention
It states, however, the present invention is not limited thereto.Test method as used in the following examples unless otherwise specified, is conventional method, is made
Raw material, reagent etc., unless otherwise specified, being can raw materials and reagents obtained from commercial sources such as regular market purchases.
Embodiment 1
Whisker loaded beta nucleating agent is obtained by portion rate 100:5, whisker selects calcium sulfate, and nucleating agent selects TMB-5；By weight
Number is measured by 100 parts of atactic copolymerized polypropenes；0.5 part of silane coupling agent；5 parts of ethylene-octene copolymer；Whisker loads β nucleation
10 parts of agent；0.5 part of antioxidant 1010,0.4 part of irgasfos 168；1.5 parts of color masterbatch are uniformly mixed drying and are extruded into pipe.
Embodiment 2
Whisker loaded beta nucleating agent is obtained by portion rate 100:6, whisker selects aluminium borate, and nucleating agent selects calcium suberate；It presses
Parts by weight are by 100 parts of atactic copolymerized polypropenes；0.6 part of rare-earth coupling agent；4 parts of ethylene-propylene-diene copolymer；Whisker
9 parts of loaded beta nucleating agent；0.8 part of antioxidant 1010；0.3 part of irgasfos 168；0.1 part of color masterbatch is uniformly mixed drying and is extruded into
Pipe.
Embodiment 3
Whisker loaded beta nucleating agent is obtained by portion rate 100:1, whisker selects calcium sulfate, and nucleating agent selects calcium pimelate；It presses
Parts by weight are by 100 parts of atactic copolymerized polypropenes；1 part of silane coupling agent；Hydrogenated styrene-butadiene-styrene tri-block
6 parts of copolymer；20 parts of whisker loaded beta nucleating agent；0.6 part of antioxidant 1010,0.4 part of irgasfos 168；5 parts of color masterbatch mixing are equal
Even drying is extruded into pipe.
Embodiment 4
Whisker loaded beta nucleating agent is obtained by portion rate 100:15, whisker selects potassium titanate, and nucleating agent selects TMB-5；By weight
Number is measured by 100 parts of atactic copolymerized polypropenes；0.7 part of aluminate coupling agent；Styrene-isoprene-phenylethene tri-block
20 parts of copolymer；8 parts of whisker loaded beta nucleating agent；0.5 part of antioxidant 1010,0.3 part of irgasfos 168；3 parts of color masterbatch mixing are equal
Even drying is extruded into pipe.
Embodiment 5
Whisker loaded beta nucleating agent, whisker selective oxidation aluminium are obtained by portion rate 100:25, nucleating agent selects calcium pimelate；
In parts by weight by 100 parts of atactic copolymerized polypropenes；5 parts of titanate coupling agent；16 parts of ethylene-octene copolymer；Whisker loads β
9 parts of nucleating agent；0.5 part of antioxidant 1010,0.4 part of irgasfos 168；1.5 parts of color masterbatch are uniformly mixed drying and are extruded into pipe.
Embodiment 6
Whisker loaded beta nucleating agent is obtained by portion rate 100:15, whisker selects calcium sulfate, and nucleating agent selects TMB-5；By weight
Number is measured by 100 parts of atactic copolymerized polypropenes；3 parts of silane coupling agent；7 parts of ethylene-octene copolymer；Whisker loaded beta nucleating agent
11 parts；0.4 part of antioxidant 1010,0.4 part of irgasfos 168；2.0 parts of color masterbatch are uniformly mixed drying and are extruded into pipe.
Comparative example 1
In parts by weight by 100 parts of atactic copolymerized polypropenes；0.5 part of antioxidant 1010,0.4 part of irgasfos 168；Color masterbatch
1.5 parts be uniformly mixed be extruded into pipe.
Comparative example 2
In parts by weight by 100 parts of atactic copolymerized polypropenes；0.5 part of silane coupling agent；9.5 parts of calcium sulfate crystal whiskers；TMB-5
0.5 part of beta nucleater；5 parts of ethylene-octene copolymer；0.5 part of antioxidant 1010,0.4 part of irgasfos 168；1.5 parts of color masterbatch mixed
It closes and is uniformly extruded into pipe.
Comparative example 3
In parts by weight by 100 parts of atactic copolymerized polypropenes；5 parts of ethylene-octene copolymer；0.5 part of silane coupling agent；It is anti-
1,010 0.5 parts of oxygen agent, 0.4 part of irgasfos 168；1.5 parts of color masterbatch be uniformly mixed be extruded into pipe.
Comparative example 4
Whisker loaded beta nucleating agent is obtained by portion rate 100:5, whisker selects calcium sulfate, and nucleating agent selects TMB-5；By weight
Number is measured by 100 parts of atactic copolymerized polypropenes；0.5 part of silane coupling agent；10 parts of whisker loaded beta nucleating agent；Antioxidant 1010
0.5 part, 0.4 part of irgasfos 168；1.5 parts of color masterbatch be uniformly mixed be extruded into pipe.
Comparative example 5
Whisker loaded beta nucleating agent is obtained by portion rate 100:0.5, whisker selects calcium sulfate, and nucleating agent selects TMB-5；It presses
Parts by weight are by 100 parts of atactic copolymerized polypropenes；0.5 part of silane coupling agent；5 parts of ethylene-octene copolymer；Whisker load β at
10 parts of core agent；0.5 part of antioxidant 1010,0.4 part of irgasfos 168；1.5 parts of color masterbatch are uniformly mixed drying and are extruded into pipe.
Comparative example 6
Whisker loaded beta nucleating agent is obtained by portion rate 100:26, whisker selects calcium sulfate, and nucleating agent selects TMB-5；By weight
Number is measured by 100 parts of atactic copolymerized polypropenes；0.5 part of silane coupling agent；5 parts of ethylene-octene copolymer；Whisker loads β nucleation
10 parts of agent；0.5 part of antioxidant 1010,0.4 part of irgasfos 168；1.5 parts of color masterbatch are uniformly mixed drying and are extruded into pipe.
Comparative example 7
Nanometer calcium carbonate loaded beta nucleating agent is obtained by portion rate 100:5, nucleating agent selects TMB-5；In parts by weight will
100 parts of atactic copolymerized polypropenes；0.5 part of silane coupling agent；5 parts of ethylene-octene copolymer；10 parts of whisker loaded beta nucleating agent；It is anti-
1,010 0.5 parts of oxygen agent, 0.4 part of irgasfos 168；1.5 parts of color masterbatch are uniformly mixed drying and are extruded into pipe.
The above various embodiments and comparative example preparation gained tubing are tested into tubing according to the method for GB/T 18743-2002
Low-temperature impact performance, test temperature are set as -10 DEG C；By GB/T 6111-2003 method, the internal pressure-resistant performance of tubing is tested.Its
Correlated performance see the table below:
The performance test of 1 Examples 1 to 6 of table and comparative example 1~7
。
It can be seen that toughener elastomer from the result of above-described embodiment and comparative example and whisker loaded beta nucleating agent be modified
The low-temperature flexibility of PPR pipe afterwards significantly improves, this shows that modified PPR pipe is obtained in the use reliability of low temperature environment
It improves.PPR pipe also has preferable pressure-resistant performance and mechanical property simultaneously.
Finally it is pointed out that above embodiments are only representative examples of the invention.Obviously, of the invention
Technical solution is not limited to above-described embodiment, can also there are many deformation.Those skilled in the art can be from the content of present invention
All deformations are directly exported or associated, are considered as scope of protection of the claims of the invention.
Claims (9)
1. a kind of PPR pipe with excellent low temperature toughness, which is characterized in that the PPR pipe is by mass fraction by following original
Material composition:
100 parts of atactic copolymerized polypropene；
0.1~5 part of coupling agent；
1~20 part of toughener；
1~20 part of whisker loaded beta nucleating agent；
0.1~3 part of antioxidant；
0.1~5 part of color masterbatch；
The mass ratio of whisker and beta nucleater is 100:1~25 in the whisker loaded beta nucleating agent.
2. according to claim 1 with the PPR pipe of excellent low temperature toughness, which is characterized in that the whisker load β nucleation
The mass ratio of whisker and beta nucleater is 100:5~15 in agent.
3. according to claim 1 with the PPR pipe of excellent low temperature toughness, which is characterized in that the whisker load β nucleation
Agent the preparation method comprises the following steps: first handle whisker surface with surface treating agent, high speed then is added in treated whisker and beta nucleater
Dispersion mixing in blender, whisker loaded beta nucleating agent obtained by drying.
4. according to claim 1 with excellent low temperature toughness PPR pipe, which is characterized in that the whisker be calcium carbonate,
One or more of aluminium borate, potassium titanate, magnesium sulfate, aluminium oxide, ZnOw.
5. according to claim 1 with the PPR pipe of excellent low temperature toughness, which is characterized in that the beta nucleater is organic
Metal carboxylate and/or amides nucleating agent.
6. according to claim 5 with the PPR pipe of excellent low temperature toughness, which is characterized in that the beta nucleater is pungent two
Sour calcium, one or more of calcium pimelate, TMB-5.
7. according to claim 1 with the PPR pipe of excellent low temperature toughness, which is characterized in that the toughener is ethylene-
Octene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene-styrene ternary block copolymer, hydrogenation of benzene second
Alkene-butadiene-styrene ternary block polymer, styrene-isoprene-phenylethene ternary block polymer, hydrogenation of benzene second
One or more of alkene-isoprene styrene ternary block polymer.
8. according to claim 1 with the PPR pipe of excellent low temperature toughness, which is characterized in that the toughener is ethylene-
Octene copolymer.
9. according to claim 1 with the PPR pipe of excellent low temperature toughness, which is characterized in that the antioxidant includes master
Antioxidant and auxiliary antioxidant, the primary antioxidant are one or more of hindered phenol or sulphur ester antioxidant, the auxiliary
Antioxidant is phosphite ester antioxidant.
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| CN201611029459.XA CN106750988B (en) | 2016-11-22 | 2016-11-22 | A kind of PPR pipe and preparation method thereof with excellent low temperature toughness |
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| CN107254101A (en) * | 2017-06-20 | 2017-10-17 | 苏州旭光聚合物有限公司 | Handle of automobile roof modified polypropene |
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| CN107857942A (en) * | 2017-12-15 | 2018-03-30 | 安徽海丰新材料科技有限公司 | A kind of PPR electric tubes formula |
| CN107903502A (en) * | 2017-12-15 | 2018-04-13 | 安徽海丰新材料科技有限公司 | A kind of PPR water pipe formula |
| CN109485996A (en) * | 2018-09-27 | 2019-03-19 | 湖北永晟塑料管业有限责任公司 | A kind of PPR pipe road of low temperature resistant cracking and preparation method thereof |
| CN109401060B (en) * | 2018-12-03 | 2020-07-31 | 四川大学 | Preparation method of aramid polyacrylamide β nucleating agent |
| CN110240755A (en) * | 2019-05-17 | 2019-09-17 | 武汉金牛经济发展有限公司 | A kind of PPR pipe with low-temperature impact resistance toughness |
| CN110343337B (en) * | 2019-08-20 | 2022-04-08 | 浙江中财管道科技股份有限公司 | Low-temperature toughened PP-R pipe and preparation method thereof |
| CN111303538A (en) * | 2020-01-16 | 2020-06-19 | 武汉金牛经济发展有限公司 | Polylactic acid modified graphene oxide oxygen-blocking pipe and preparation method thereof |
| CN111518339B (en) * | 2020-05-05 | 2022-12-16 | 上海齐润新材料有限公司 | Low-temperature-resistant reinforced polypropylene plastic pipe and preparation method thereof |
| CN112430365A (en) * | 2020-11-24 | 2021-03-02 | 武汉金牛经济发展有限公司 | Anti-scale PPR (polypropylene random copolymer) pipe with low-temperature toughness and preparation method thereof |
| CN113072770A (en) * | 2021-04-19 | 2021-07-06 | 茂名联塑建材有限公司 | Toughened heat-resistant PPR pipe and preparation method and application thereof |
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| CN115304867A (en) * | 2021-05-06 | 2022-11-08 | 中国石油天然气股份有限公司 | Special resin for toughened PPR (polypropylene random copolymer) pipe and preparation method thereof |
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