CN103554673A - Toughened and modified pentatricopeptide repeats (PPR) extrusion pipe material and preparation method thereof - Google Patents
Toughened and modified pentatricopeptide repeats (PPR) extrusion pipe material and preparation method thereof Download PDFInfo
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- CN103554673A CN103554673A CN201310509303.1A CN201310509303A CN103554673A CN 103554673 A CN103554673 A CN 103554673A CN 201310509303 A CN201310509303 A CN 201310509303A CN 103554673 A CN103554673 A CN 103554673A
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
-
- 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
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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
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to the technical field of toughened and modified pentatricopeptide repeats (PPR), and discloses a toughened and modified PPR extrusion pipe material and a preparation method thereof. The toughened and modified PPR extrusion pipe material comprises the following components by mass percent: 58-98% of PPR, 1-20% of a toughening agent, 1-20% of poly 1-butene, 0-1% of a heat stabilizer and 0-1% of a nucleating agent special for polypropylene. According to the method, synergistic toughening of the traditional toughening agent and novel toughening agent of poly 1-butene is adopted, so that the low-temperature toughness of the PPR extrusion pipe material is improved, and the welding strength and heat resistance are ensured. The tensile strength at 23 DEG C is greater than or equal to 25MPa, the elongation at break at 23 DEG C is greater than or equal to 500%, the tensile strength at 95 DEG C is greater than or equal to 10MPa, the low-temperature notch impact strength at 30 DEG C below zero is greater than or equal to 5KJ/m<2>, and the vicat softening temperature (10N) is greater than or equal to 125 DEG C.
Description
Technical field
The invention belongs to toughening modifying PPR technical field, particularly a kind of toughening modifying PPR extruding pipe material and preparation method thereof.
Background technology
PPR is again three type polypropylene tube, atactic copolymerized polypropene, adopts atactic copolymerized polypropene through being extruded as tubing, and injection moulding becomes pipe fitting.It is the novel plastic pipeline product of Europe Application and Development at the beginning of the nineties.PPR is the end of the eighties, adopts gas-phase copolymerization technique to make 5% left and right PE homogeneous polymerization and become pipeline material of new generation randomly in PP molecular chain.Its intensity is high, has good shock resistance and long-term creep behaviour.Pipeline has excellent chemically-resistant article corrosive nature simultaneously, is insoluble to any known solvent under normal temperature, so except house ornamentation, be more suitable for the places such as chemical plant and carry chemical fluid.Work-ing life can be for 50 years.
But the fatal shortcoming of PPR tubing is that low-temperature flexibility is poor, when envrionment temperature is during lower than 0 ℃, low-temperature flexibility sharply declines.For solving this defect, there is research to adopt ethylene-octene copolymer (POE) Toughened PP R tubing to improve its low-temperature flexibility, but adopt this kind of method on the one hand the thermotolerance of PPR tubing can decline significantly, and the welding strength of PPR tubing, rigidity can be greatly affected.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of toughening modifying PPR extruding pipe material.The present invention adopts traditional toughner to improve the low-temperature flexibility of PPR, simultaneously for making up high heat resistance that traditional toughner causes and the decline of welding strength, adopt poly 1-butene that weldability, thermotolerance and winter hardiness are all excellent as synergistic toughner, except improving the low-temperature flexibility of PPR tubing, also improved greatly welding strength and the thermotolerance of PPR.
Another object of the present invention is to provide a kind of preparation method of above-mentioned toughening modifying PPR extruding pipe material.
Still a further object of the present invention is to provide the application of above-mentioned toughening modifying PPR extruding pipe material in Indoor environment hot water pipe.
Object of the present invention realizes by following proposal:
A PPR extruding pipe material, the component that comprises following massfraction:
Preferably, described PPR refers to that melt flow rate (MFR) is the atactic copolymerized polypropene of 0.1～1g/10min.
Preferably, described toughner is at least one in ethylene-octene copolymer, ethylene-propylene-butadienecopolymer, styrene-butadiene-styrene ternary block polymer (SBS), hydrogenated styrene-butadiene-styrene ternary block polymer (SEBS), styrene-isoprene-phenylethene ternary block polymer (SIS), hydrogenated styrene-isoprene-polystyrene ternary segmented copolymer (SEPS).
Preferably, described poly 1-butene refers to that melt flow rate (MFR) is the extrusion grade poly 1-butene of 0.1～2g/10min.
Poly 1-butene has excellent high-low temperature resistant characteristic, maximum operation (service) temperature can reach 110 ℃, and still there is excellent toughness at-30 ℃, there is excellent consistency with various polyolefine materials and olefin type elastomer simultaneously, be widely used as compatible polyolefin agent, be therefore known as the gold in plastics.The present invention has utilized polyolefinic above-mentioned advantage just, the compatilizer between PPR and traditional toughner has just well been played in a small amount of interpolation, think that with traditional toughner synergy makes traditional toughner better bring into play toughening effect, thereby reduce the consumption of traditional toughner, prevent the reduction of material welding strength and rigidity, obtain the PPR extruding pipe material of toughening modifying.
Described thermo-stabilizer refers to the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and at least one in calixarene kind thermo-stabilizer.
The effect of thermo-stabilizer is to suppress the degraded that in the course of processing, polymkeric substance produces.
The special-purpose nucleator of described polypropylene refers at least one in talcum powder, glucitols and organic phosphate.
The effect of the special-purpose nucleator of polypropylene is in order to improve the crystallization rate in material injection moulding process, shortening injection molding cycle.
The present invention also provides a kind of preparation method of above-mentioned toughening modifying PPR extruding pipe material, comprises following concrete steps:
The special-purpose nucleator of PPR, toughner, poly 1-butene, thermo-stabilizer and polypropylene melting mixing in forcing machine is disperseed, and each section of temperature of forcing machine is arranged on 220～260 ℃, and extruding pelletization obtains toughening modifying PPR extruding pipe material.
Preferably, described forcing machine refers to that length-to-diameter ratio is the twin screw extruder of 40:1.
The present invention also provides the application of above-mentioned toughening modifying PPR extruding pipe material in interior architecture hot water pipe.
Mechanism of the present invention is:
The present invention adopts the method for traditional toughner and new type of toughening agent poly 1-butene coordination plasticizing, has both effectively improved the low-temperature flexibility of PPR tubing, has guaranteed again its welding strength and thermotolerance simultaneously.Poly 1-butene and PPR and traditional toughner have good consistency, therefore can be used as the compatilizer between PPR and traditional toughner, make traditional toughner better bring into play toughening effect with the synergy of traditional toughner, therefore can reduce greatly the consumption of traditional toughner, prevent that the rigidity of PPR tubing from reducing.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) the present invention adopts the method for traditional toughner and new type of toughening agent poly 1-butene coordination plasticizing, has both effectively improved the low-temperature flexibility of PPR extruding pipe material, has guaranteed again its welding strength and thermotolerance simultaneously.
(2) toughening modifying PPR extruding pipe material of the present invention had both had excellent low-temperature flexibility, there is again excellent welding strength and thermotolerance, can meet the requirement to PPR tubing in low temperature environment, its tensile strength (23 ℃)>=25MPa, elongation at break (23 ℃)>=500%,, tensile strength (95 ℃)>=10MPa, low temperature notched shock strength (30 ℃)>=5KJ/m
2, vicat softening temperature (10N)>=125 ℃.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: comparative example 1
In the twin screw extruder that is 40:1 in length-to-diameter ratio by 99.7 kilograms of polypropylene PP R4220, the special-purpose nucleator TMP-5 of 168,0.1 kilogram of polypropylene of 1010,0.1 kilogram of thermo-stabilizer of 0.1 kilogram of thermo-stabilizer, melting mixing is disperseed, each section of temperature of forcing machine is arranged on 220～260 ℃, extruding pelletization, obtains product.
Embodiment 2: comparative example 2
In the twin screw extruder that is 40:1 in length-to-diameter ratio by 89.7 kilograms of polypropylene PP R4220,10 kilograms of ethylene-octene copolymer POE DF610, the special-purpose nucleator TMP-5 of 168,0.1 kilogram of polypropylene of 1010,0.1 kilogram of thermo-stabilizer of 0.1 kilogram of thermo-stabilizer, melting mixing is disperseed, each section of temperature of forcing machine is arranged on 220～260 ℃, extruding pelletization, finally obtains product.
Embodiment: 3: the preparation of toughening modifying PPR extruding pipe material
In the twin screw extruder that is 40:1 in length-to-diameter ratio by 94.5 kilograms of polypropylene PP R4220,5 kilograms of ethylene-octene copolymer POE DF610,5 kilograms of polybutene PB-10850M, the special-purpose nucleator TMP-5 of 168,0.1 kilogram of polypropylene of 1010,0.1 kilogram of thermo-stabilizer of 0.1 kilogram of thermo-stabilizer, melting mixing is disperseed, each section of temperature of forcing machine is arranged on 220～260 ℃, extruding pelletization, finally obtains product.
Embodiment 4: the preparation of toughening modifying PPR extruding pipe material
In the twin screw extruder that is 40:1 in length-to-diameter ratio by 81.2 kilograms of polypropylene PP R200P, 8 kilograms of styrenic elastomerics SEPTON2063,10 kilograms of polybutene PB-1DP9217M, the special-purpose nucleator TMP-5 of 168,0.2 kilogram of polypropylene of 1010,0.3 kilogram of thermo-stabilizer of 0.3 kilogram of thermo-stabilizer, melting mixing is disperseed, each section of temperature of forcing machine is arranged on 220～260 ℃, extruding pelletization, finally obtains product.
Embodiment 5: the preparation of toughening modifying PPR extruding pipe material
In the twin screw extruder that is 40:1 in length-to-diameter ratio by 74 kilograms of polypropylene PP R200P, 10 kilograms of styrenic elastomerics SEBS6006,15 kilograms of polybutene PB-1DP8911M, the special-purpose nucleator TMP-5 of 168,0.2 kilogram of polypropylene of 1010,0.4 kilogram of thermo-stabilizer of 0.4 kilogram of thermo-stabilizer, melting mixing is disperseed, each section of temperature of forcing machine is arranged on 220～260 ℃, extruding pelletization, finally obtains product.
Embodiment 6: the performance index of toughening modifying PPR extruding pipe material
The PPR material that embodiment 1～5 is prepared carries out performance measurement, testing standard: tensile strength ISO527/2-93; Elongation at break ISO527/2-93; Low temperature notched shock strength (30 ℃) ISO180-93; Vicat softening temperature ISO306.Test result is in Table 1.
The performance index of table 1 toughening modifying PPR extruding pipe material
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength (23 ℃)/MPa | 28.5 | 24 | 26.5 | 27 | 28 |
| Elongation at break (23 ℃)/% | 300 | 520 | 700 | 750 | 800 |
| Tensile strength (95 ℃)/MPa | 14.9 | 8.7 | 14.3 | 15.9 | 16.9 |
| Low temperature notched shock strength/KJ/m 2 | 3.2 | 5.5 | 6.2 | 7.5 | 8.9 |
| Vicat softening temperature (10N)/℃ | 132 | 120 | 130 | 133 | 135 |
From table 1, adopt poly 1-butene synergistic Toughened PP R tubing, do not affecting under the prerequisite of rigidity of material, by adding a small amount of poly 1-butene, can realize the remarkable increase of toughness of material.Both effectively improve the low-temperature flexibility of PPR extruding pipe material, guaranteed again its welding strength and thermotolerance simultaneously.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. a toughening modifying PPR extruding pipe material, is characterized in that the component that comprises following massfraction:
2. toughening modifying PPR extruding pipe material according to claim 1, is characterized in that: described PPR refers to that melt flow rate (MFR) is the atactic copolymerized polypropene of 0.1～1g/10min.
3. toughening modifying PPR extruding pipe material according to claim 1, is characterized in that: described toughner is at least one in ethylene-octene copolymer, ethylene-propylene-butadienecopolymer, styrene-butadiene-styrene ternary block polymer, hydrogenated styrene-butadiene-styrene ternary block polymer, styrene-isoprene-phenylethene ternary block polymer, hydrogenated styrene-isoprene-polystyrene ternary segmented copolymer.
4. toughening modifying PPR extruding pipe material according to claim 1, is characterized in that: described poly 1-butene refers to that melt flow rate (MFR) is the extrusion grade poly 1-butene of 0.1～2g/10min.
5. toughening modifying PPR extruding pipe material according to claim 1, is characterized in that: described thermo-stabilizer refers to the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and at least one in calixarene kind thermo-stabilizer.
6. toughening modifying PPR extruding pipe material according to claim 1, is characterized in that: the special-purpose nucleator of described polypropylene refers at least one in talcum powder, glucitols and organic phosphate.
7. according to a preparation method for the toughening modifying PPR extruding pipe material described in claim 1～6 any one, it is characterized in that comprising following concrete steps:
The special-purpose nucleator of PPR, toughner, poly 1-butene, thermo-stabilizer and polypropylene melting mixing in forcing machine is disperseed, and each section of temperature of forcing machine is arranged on 220～260 ℃, and extruding pelletization obtains toughening modifying PPR extruding pipe material.
8. the preparation method of toughening modifying PPR extruding pipe material according to claim 7, is characterized in that: described forcing machine refers to that length-to-diameter ratio is the twin screw extruder of 40:1.
9. the application in interior architecture hot water pipe according to the toughening modifying PPR extruding pipe material described in claim 1～6 any one.
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| CN201310509303.1A CN103554673A (en) | 2013-10-25 | 2013-10-25 | Toughened and modified pentatricopeptide repeats (PPR) extrusion pipe material and preparation method thereof |
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| CN201310509303.1A CN103554673A (en) | 2013-10-25 | 2013-10-25 | Toughened and modified pentatricopeptide repeats (PPR) extrusion pipe material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497423A (en) * | 2014-12-04 | 2015-04-08 | 联塑科技发展(武汉)有限公司 | Impact-resistant PP-R tube and preparation method thereof |
| CN105440549A (en) * | 2015-12-14 | 2016-03-30 | 上海金发科技发展有限公司 | Scratch-resistant super-toughness automotive interior polypropylene material and preparation method thereof |
| CN106352163A (en) * | 2016-08-29 | 2017-01-25 | 飞雕电器集团有限公司 | Low temperature impact resistant composite polypropylene random |
| CN109401072A (en) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A kind of high cold-resistant PPR hot water tube material and preparation method thereof |
| CN112175299A (en) * | 2019-07-01 | 2021-01-05 | 现代自动车株式会社 | Pipe composition for vehicle using ratproof agent and preparation method thereof |
| CN115008837A (en) * | 2022-06-13 | 2022-09-06 | 安徽源锂高新材料有限公司 | Enhanced POPB1-M double-color pipe and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497423A (en) * | 2014-12-04 | 2015-04-08 | 联塑科技发展(武汉)有限公司 | Impact-resistant PP-R tube and preparation method thereof |
| CN105440549A (en) * | 2015-12-14 | 2016-03-30 | 上海金发科技发展有限公司 | Scratch-resistant super-toughness automotive interior polypropylene material and preparation method thereof |
| CN105440549B (en) * | 2015-12-14 | 2017-11-17 | 上海金发科技发展有限公司 | A kind of scratch-resistant, ultra-tough automotive trim polypropylene material and preparation method thereof |
| CN106352163A (en) * | 2016-08-29 | 2017-01-25 | 飞雕电器集团有限公司 | Low temperature impact resistant composite polypropylene random |
| CN109401072A (en) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A kind of high cold-resistant PPR hot water tube material and preparation method thereof |
| CN112175299A (en) * | 2019-07-01 | 2021-01-05 | 现代自动车株式会社 | Pipe composition for vehicle using ratproof agent and preparation method thereof |
| CN115008837A (en) * | 2022-06-13 | 2022-09-06 | 安徽源锂高新材料有限公司 | Enhanced POPB1-M double-color pipe and preparation method thereof |
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Application publication date: 20140205 |