CN101338053A - Polyolefine core tube and method for preparing same - Google Patents
Polyolefine core tube and method for preparing same Download PDFInfo
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- CN101338053A CN101338053A CNA200810021634XA CN200810021634A CN101338053A CN 101338053 A CN101338053 A CN 101338053A CN A200810021634X A CNA200810021634X A CN A200810021634XA CN 200810021634 A CN200810021634 A CN 200810021634A CN 101338053 A CN101338053 A CN 101338053A
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Abstract
The invention discloses a polyolefin core pipe and a preparation method thereof. The core pipe is obtained by mixing two kinds of high isotacticity of propylene homopolymers according to the weight proportion of 1 to 45 : 99 to 55 and adding maleic anhydride grafted polypropylene and flow processing aids for mixing evenly and through two-steps extrusion, cooling, extension, molding and cutting. The invention adopts the two kinds of high isotacticity of propylene resin with different molecular weights and the flow processing aids to promote the polymer macromolecule chain nucleation and the chain migration and diffusive capacity, speeds up polypropylene crystallization process and improves the processability and the mechanical property of polyolefin; the maleic anhydride grafted polypropylene and a filling reinforcing system intensify the physical and chemical action between fillers and polypropylene resin and between polypropylene resin to strengthen the hardness, rigidity and durability of polypropylene tubular products. The prepared core pipe with 75mm to 360mm of inside diameter and 7mm to 30mm of wall thickness can replace various paper core pipes, thereby having a wide popularization and application prospect.
Description
Technical field
The present invention relates to a kind of polyolefin pipe and preparation method thereof, particularly a kind of polyolefine core tube of paper or textiles etc. and preparation method thereof of reeling that is used to belongs to technical field of polymer materials.
Background technology
In recent years, polyolefine catalyst for synthesizing and polymerization technique development are rapidly, technical elements at the high rigidity polyolefin pipe of preparation, Chinese invention patent " high resistance polypropylene tube " (CN1133840C) provides a kind of high modulus in tension that has, high notched Izod impact strength, the polypropylene tube of the high resistibility performance of high ring rigidity and impact load.On technical scheme, this tubing is made of A and two kinds of components of B, A is that the isotactic polypropylene homopolymer of 80～98 mass fractions is as the bonding matrix component, its ten regularities are greater than 95%, B be 2～20% mass fractions by the propylene of 50～70 mass fractions and ethene and/or other C of 30～50 mass fractions
4～C
8The multipolymer that generates of alpha-olefin as the elastomerics composition of discrete distribution, the ring stiffness of this polypropylene tube satisfies 110 (10/ (SDR-1))
3≤ SN≤190 (10/ (SDR-1))
3, unit is kN/m
2, SDR is the ratio of external diameter and wall thickness, testing method ISO9969 (probe temperature is 23 ℃).When external diameter is 170 millimeters, when wall thickness was 11 millimeters, its ring stiffness was 36～63kN/m
2, preferably at 45～54kN/m
2This polypropylene tube only is suitable for the waste pipe system.
In industries such as weaving, papermaking, the wireline reel when being extensive use of the core pipe as cloth or paper product packing, different with common pipeline, the core pipe is had higher ring stiffness requirement, especially at paper industry.At present, dull relatively in the widely used paper core section product of paper industry type, mainly be the papery paper tube.Paper tube exists not only that production efficiency is low, production process is complicated, and production cost height, cost performance are low etc.; On the other hand, paper tube itself moist distortion can occur, cause rigidity and intensity sharply to descend the degradation defective.For example, when relative humidity in the air when 50% increases to 75%, the equilibrium moisture content of paper tube then increases to 11.5% from 7.5%, then the intensity of paper tube then descends about 15%.This situation has restricted the high speed of a motor vehicle, the high efficiency demand for development of papermaking when wide format and production, therefore, pressing for provides a kind of have rigidity height, chemical stability is good, heat-drawn wire is high and fatigue performance is good core tube material, especially will be applicable to the coil paper core pipe of paper industry.
Summary of the invention
In order to overcome the deficiency that prior art exists, the purpose of this invention is to provide a kind of mechanical property and resistance to fatigue excellence, and production cost is low, production process is easy, the polyolefine core tube of asepsis environment-protecting and preparation method thereof.
For achieving the above object, the technical solution adopted in the present invention is: provide a kind of polyolefine core tube, by weight, its component comprises: 100 parts of the polypropylene of degree of isotacticity 〉=95%, 1～20 part of maleic anhydride inoculated polypropylene, 2.5～10 parts of tougheners, 1～40 part of filler, 0.1～5 part of mobile processing aid, 0.1～1.5 part of α nucleator, 0.1～2 part in oxidation inhibitor, organo-silicon coupling agent, consumption is 1～30% of a filler, and catalyzer, consumption are 0.1～20% of organo-silicon coupling agent; The polypropylene of described degree of isotacticity 〉=95% comprises (230 ℃ of melt flow indexes, 2.16kg) be the high molecular weight polypropylene of 0.1～1.0g/10min and the lower molecular weight polypropylene that melt flow index is 1.0～6.0g/10min, their weight ratio is 1～45: 99～55; Described maleic anhydride inoculated polypropylene is maleic anhydride grafting ratio 0.3～1.5%, melt flow index (230 ℃ 2.16kg) are the polypropylene of 5～45g/10min; Described toughener is N, N '-4,4 '-diphenyl methane dimaleimide or N, a kind of in the N '-penylene bismaleimides.
Described filler is lime carbonate, talcum powder, kaolin, glass fibre, short carbon fiber or its combination.
Described organo-silicon coupling agent is a kind of in vinyl silicane coupling agent, acryloxy silane coupling agent, amino silicane coupling agent or the epoxy silane coupling.
Described catalyzer is a kind of in Dibutyltin oxide, dibutyl tin dilaurate or the stannous octoate.
Described mobile processing aid is silicone resin, fluoropolymer auxiliary agent.
Described α nucleator is carboxylic metallic salt, phosphate metal salt, dibenzyl sorbyl alcohol or derivatives thereof.
Described oxidation inhibitor is oxidation inhibitor 168, antioxidant 1010, antioxidant 1076 or its combination.
The internal diameter of described core pipe is 7～30 millimeters of 75～360 millimeters, wall thickness.
A kind of method for preparing said polyolefins core pipe, its step is as follows:
1) by weight, after the organo-silicon coupling agent high-speed mixing processing with 1～40 part of filler and amount of filler 1～30%, handle with the catalyzer high-speed mixing of 1～20 part of maleic anhydride inoculated polypropylene, 2.5～10 parts of tougheners and organo-silicon coupling agent consumption 0.1～20% again, obtain filling and the enhancing system;
2) by weight, with (230 ℃ of 1～45 part of degree of isotacticity 〉=95% melt flow index, 2.16kg) be the high molecular weight polypropylene of 0.1～1.0g/10min, 0.1～5 part of mobile processing aid, 0.1～1.5 portion of α nucleator and oxidation inhibitor high-speed mixing, extruding pelletization then, pellet A;
3) (230 ℃ is that lower molecular weight polypropylene and the oxidation inhibitor of 1.0～6.0g/10min carries out high-speed mixing, extruding pelletization B 2.16kg) for the pellet A that obtains of the filling that step 1 is obtained and enhancing system, step 2,99～55 parts of degree of isotacticity 〉=95% melt flow indexes; In step 2 and the step 3, by weight, polyacrylic total amount is 100 parts, and the total amount of oxidation inhibitor is 0.1～2 part.
4) with pellet B through extruding, after cooling, drawing-off, typing and the cutting, obtaining polyolefine core tube.
Compared with prior art, the present invention has following advantage:
1, the present invention uses the high isotatic polypropylene resin of two kinds of melt flow indexes, flow modifier auxiliary agent to promote polymer macromolecule chain nucleation and chain diffusion mobility ability, accelerates the crystalling propylene process, thereby improves polyolefinic processibility and mechanical property.
2, the present invention has strengthened physics and chemical action between filler and the acrylic resin, between the acrylic resin by toughener, filler and organo-silicon coupling agent, maleic anhydride inoculated polypropylene, thus intensity, rigidity and the resistance to fatigue of Reinforced Polypropylene refill tubing.
3, the present invention is a base material with the thermoplastic polypropylene resin, adopts extruding forming method, the production efficiency height, and easy to operate, production process is pollution-free, has vast market prospect.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1:
Composition of raw materials
(230 ℃ is 0.1 2.16kg) to the MFI of high molecular isotatic polypropylene, and degree of isotacticity is 96%, and the MFI of lower molecular weight isotatic polypropylene is 3.5, and degree of isotacticity is 96%, and high and low molecular weight polypropylene weight ratio is 10: 90; The 8phr maleic anhydride inoculated polypropylene, its weight percentage of grafting is 1%, MFI (230 ℃ 2.16kg) are 40g/10min; 3phr toughener N, N '-4,4 '-diphenyl methane dimaleimide; The 23phr filler, wherein, 23ph r is talcum powder (1000 order); 3phr is filler short carbon fiber (15 microns of Fibre diameters, 0.5 millimeter of a staple length); Organo-silicon coupling agent is an amino silicane coupling agent, and it is 15% that its consumption accounts for the filler weight ratio, and the catalyzer Dibutyltin oxide occupies 10% of machine silicone couplet weight; α nucleator carboxylic metallic salt 0.5phr; Processing aid silicone resin 1.5phr flows; Oxidation inhibitor 168 add-ons are 1phr; Pigment is a small amount of.
Core control is equipped with
1, filling mixes with the enhancing system:
Filler and organo-silicon coupling agent are carried out the high-speed mixing processing, handle with maleic anhydride inoculated polypropylene, toughener and catalyzer high-speed mixing again, must strengthen and infill system.
2, high molecular polyolefine granulation:
With high molecular isotatic polypropylene, flow processing aid, α nucleator and oxidation inhibitor high-speed mixing, extruding pelletization gets pellet A then.
3, polyolefin pellets preparation:
Pellet A, low-molecular-weight polypropylene, oxidation inhibitor, pigment that the enhancing that step 1 is obtained and infill system, step 2 obtain carry out high-speed mixing, extruding pelletization B;
In step 2 and the step 3, the ratio of added quantity of antioxidant is identical with the ratio of high and low molecular weight polypropylene.
4, tubulation
The pellet B that step 3 is obtained extrudes, cooling, drawing-off, typing and cutting, the polyolefin core tube material, the product of 75～360 millimeters of its internal diameters, 7～30 millimeters of wall thickness.
Embodiment 2
The MFI of high molecular isotatic polypropylene is 0.5, and degree of isotacticity is 96%, and the MFI of lower molecular weight isotatic polypropylene is 3.0, and degree of isotacticity is 96%, and high and low molecular weight polypropylene weight ratio is 15: 85; Its weight percentage of grafting of maleic anhydride inoculated polypropylene is 1%, and MFI (230 ℃, 2.16kg) be 30g/10min, add-on is 10phr; Toughener N, N '-4,4 '-diphenyl methane dimaleimide 5phr; Filler glass fibre (5 microns of Fibre diameters) consumption is 18phr; Organo-silicon coupling agent is an epoxy silane coupling, and its consumption accounts for 10% of filler weight, and the catalyzer dibutyl tin laurate occupies 13% of machine silicone couplet weight; Mobile processing aid is fluoropolymer 1phr; The α nucleator is dibenzyl sorbyl alcohol or its derivative, and add-on is 0.5phr; Oxidation inhibitor is the composition of antioxidant 1010 and antioxidant 1076, and consumption is 1phr; Pigment is a small amount of.
The preparation process of core tube material is with embodiment 1.
Embodiment 3
The MFI of high molecular isotatic polypropylene is 0.5, and degree of isotacticity is 96%, and the MFI of lower molecular weight isotatic polypropylene is 3.0, and degree of isotacticity is 96%, and high and low molecular weight polypropylene weight ratio is 30: 70; Its weight percentage of grafting of maleic anhydride inoculated polypropylene is 1%, and MFI (230 ℃, 2.16kg) be 15g/10min, add-on is 12phr; Toughener N, a N '-penylene bismaleimides 4phr; Amount of filler 20phr, wherein glass fibre (5 microns of Fibre diameters) consumption is 15phr, short carbon fiber (15 microns of Fibre diameters, 0.5 millimeter of staple length) 5phr; Organo-silicon coupling agent is the acryloxy silane coupling agent, and its consumption accounts for 20% of filler weight, and the inferior tin of octoate catalyst occupies 10% of machine silicone couplet weight; Processing aid fluoropolymer 1.5phr flows; The α nucleator is phosphate metal salt or its derivative, and consumption is 0.5phr; Oxidation inhibitor is antioxidant 1076, and consumption is 0.5phr; Pigment is a small amount of.
The preparation process of core tube material is with embodiment 1.
Test and do the performance comparison with polypropylene cores pipe and conventional polypropylene tube sample (reference examples) that the foregoing description 1～3 technical scheme makes, 170 millimeters of sample pipe internal diameters, 11 ± 1 millimeters of wall thickness, the result is referring to table one.
The component of reference examples sample is: the MFI of isotatic polypropylene is 2.5, and degree of isotacticity is 96%, α nucleator 0.5phr, and oxidation inhibitor 0.5phr, pigment is a small amount of; The direct high-speed mixing of raw material, extrude, cooling, drawing-off and cutting, the polyolefin core tube material.
Table 1:
| Pipe performance | Testing method | Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples |
| Flexural strength, Mpa | GB/T9341-2000 | 64 | 64 | 63 | 56 |
| Tensile strength, Mpa | GB/T1040-1992 | 37 | 36 | 37 | 33 |
| Ring stiffness, kN/m 2 | GB/T9647-2003 | 73 | 75 | 82 | 45 |
| Vicat softening temperature, ℃ | GB/T8802-2001 | 158 | 156 | 160 | 150 |
As can be seen from Table 1: technical solution of the present invention is used two kinds of isotatic polypropylene, maleic anhydride inoculated polypropylene, filler, toughener, organo-silicon coupling agent and mobile processing aid compositions, vicat softening temperature, flexural strength and the tensile strength of polyolefine core tube have not only been improved, the most important thing is to have improved greatly the ring stiffness of tubing, therefore, polypropylene cores pipe provided by the invention can replace existing various papery core pipes fully, is with a wide range of applications at weaving and paper industry.
Claims (9)
1. a polyolefine core tube is characterized in that by weight, and its component comprises: 100 parts of the polypropylene of degree of isotacticity 〉=95%, 1～20 part of maleic anhydride inoculated polypropylene, 2.5～10 parts of tougheners, 1～40 part of filler, 0.1～5 part of mobile processing aid, 0.1～1.5 part of α nucleator, 0.1～2 part in oxidation inhibitor, organo-silicon coupling agent, consumption are 1～30% of filler, catalyzer, consumption are 0.1～20% of organo-silicon coupling agent; The polypropylene of described degree of isotacticity 〉=95% comprises (230 ℃ of melt flow indexes, 2.16kg) be the high molecular weight polypropylene of 0.1～1.0g/10min and the lower molecular weight polypropylene that melt flow index is 1.0～6.0g/10min, their weight ratio is 1～45: 99～55; Described maleic anhydride inoculated polypropylene is maleic anhydride grafting ratio 0.3～1.5%, melt flow index (230 ℃ 2.16kg) are the polypropylene of 5～45g/10min; Described toughener is N, N '-4,4 '-diphenyl methane dimaleimide or N, a kind of in the N '-penylene bismaleimides.
2. a kind of polyolefine core tube according to claim 1 is characterized in that: described filler is lime carbonate, talcum powder, kaolin, glass fibre, short carbon fiber or its combination.
3. a kind of polyolefine core tube according to claim 1 is characterized in that: described organo-silicon coupling agent is a kind of in vinyl silicane coupling agent, acryloxy silane coupling agent, amino silicane coupling agent or the epoxy silane coupling.
4. a kind of polyolefine core tube according to claim 1 is characterized in that: described catalyzer is a kind of in Dibutyltin oxide, dibutyl tin dilaurate or the stannous octoate.
5. a kind of polyolefine core tube according to claim 1 is characterized in that: described mobile processing aid is silicone resin, fluoropolymer auxiliary agent.
6. a kind of polyolefine core tube according to claim 1 is characterized in that: described α nucleator is carboxylic metallic salt, phosphate metal salt, dibenzyl sorbyl alcohol or derivatives thereof.
7. a kind of polyolefine core tube according to claim 1 is characterized in that: described oxidation inhibitor is oxidation inhibitor 168, antioxidant 1010, antioxidant 1076 or its combination.
8. a kind of polyolefine core tube according to claim 1 is characterized in that: the internal diameter of described core pipe is 7～30 millimeters of 75～360 millimeters, wall thickness.
9. method for preparing the described polyolefine core tube of claim 1 is characterized in that the step of this method is as follows:
1) by weight, after the organo-silicon coupling agent high-speed mixing processing with 1～40 part of filler and amount of filler 1～30%, handle with the catalyzer high-speed mixing of 1～20 part of maleic anhydride inoculated polypropylene, 2.5～10 parts of tougheners and organo-silicon coupling agent consumption 0.1～20% again, obtain filling and the enhancing system;
2) by weight, with (230 ℃ of 1～45 part of degree of isotacticity 〉=95% melt flow index, 2.16kg) be the high molecular weight polypropylene of 0.1～1.0g/10min, 0.1～5 part of mobile processing aid, 0.1～1.5 portion of α nucleator and oxidation inhibitor high-speed mixing, extruding pelletization then, pellet A;
3) (230 ℃ is that lower molecular weight polypropylene and the oxidation inhibitor of 1.0～6.0g/10min carries out high-speed mixing, extruding pelletization B 2.16kg) for the pellet A that obtains of the filling that step 1 is obtained and enhancing system, step 2,99～55 parts of degree of isotacticity 〉=95% melt flow indexes; In step 2 and the step 3, by weight, polyacrylic total amount is 100 parts, and the total amount of oxidation inhibitor is 0.1～2 part;
4) with pellet B through extruding, after cooling, drawing-off, typing and the cutting, obtaining polyolefine core tube.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086280A (en) * | 2009-12-04 | 2011-06-08 | 中国石油化工股份有限公司 | Preparation method of polypropylene nano composite material |
| CN101698736B (en) * | 2009-10-30 | 2011-10-05 | 华南理工大学 | Modification method for enhancing polarity and flowability of polypropylene |
| CN103289183A (en) * | 2012-02-23 | 2013-09-11 | 合肥杰事杰新材料股份有限公司 | Thermal enhancement polypropylene and preparation method thereof |
| CN103382274A (en) * | 2013-08-05 | 2013-11-06 | 广州赫尔普化工有限公司 | Compound additive for polypropylene block copolymer (PPB) |
| CN103694566A (en) * | 2013-11-30 | 2014-04-02 | 吉林省松花湖管业有限公司 | Carbon fiber reinforced polypropylene material and application thereof to pipeline |
| CN103804741A (en) * | 2014-01-10 | 2014-05-21 | 芜湖新磊塑胶科技有限公司 | Ceramic sculpture material as well as preparation method and application thereof |
| CN104476788A (en) * | 2014-12-05 | 2015-04-01 | 黑龙江安瑞佳新材料科技开发有限公司 | Glass fiber reinforced polypropylene pipe production device and glass fiber reinforced polypropylene pipe production process |
| CN105179824A (en) * | 2015-11-04 | 2015-12-23 | 南京晟林再生资源有限公司 | High-strength wear resistant plastic pipe |
| WO2016201621A1 (en) * | 2015-06-16 | 2016-12-22 | Borouge Compounding Shanghai Co., Ltd. | Polypropylene composition for pipe applications |
| CN106751354A (en) * | 2016-12-31 | 2017-05-31 | 天津科彩塑料科技有限公司 | A kind of core layer material and preparation method thereof |
| CN109370053A (en) * | 2018-10-24 | 2019-02-22 | 江苏亿超工程塑料有限公司 | A kind of high rigidity polypropylene paper core pipe and preparation method thereof |
| CN110014696A (en) * | 2019-03-01 | 2019-07-16 | 日丰企业集团有限公司 | PA tube of high-strength anti-flaming and preparation method thereof |
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| CN1247207A (en) * | 1999-09-24 | 2000-03-15 | 中国科学院化学研究所 | Polypropylene composition and its pipes |
| CN101153096A (en) * | 2006-09-28 | 2008-04-02 | 上海普利特复合材料有限公司 | Heat oxidization, ultraviolet light resistant glass fiber reinforced polypropylene composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101698736B (en) * | 2009-10-30 | 2011-10-05 | 华南理工大学 | Modification method for enhancing polarity and flowability of polypropylene |
| CN102086280B (en) * | 2009-12-04 | 2014-04-16 | 中国石油化工股份有限公司 | Preparation method of polypropylene nano composite material |
| CN102086280A (en) * | 2009-12-04 | 2011-06-08 | 中国石油化工股份有限公司 | Preparation method of polypropylene nano composite material |
| CN103289183A (en) * | 2012-02-23 | 2013-09-11 | 合肥杰事杰新材料股份有限公司 | Thermal enhancement polypropylene and preparation method thereof |
| CN103289183B (en) * | 2012-02-23 | 2016-06-15 | 合肥杰事杰新材料股份有限公司 | A kind of hot RPP and preparation method thereof |
| CN103382274A (en) * | 2013-08-05 | 2013-11-06 | 广州赫尔普化工有限公司 | Compound additive for polypropylene block copolymer (PPB) |
| CN103382274B (en) * | 2013-08-05 | 2016-01-20 | 广州赫尔普化工有限公司 | A kind of block copolymerization polypropylene composite additive |
| CN103694566A (en) * | 2013-11-30 | 2014-04-02 | 吉林省松花湖管业有限公司 | Carbon fiber reinforced polypropylene material and application thereof to pipeline |
| CN103804741B (en) * | 2014-01-10 | 2016-08-17 | 芜湖新磊塑胶科技有限公司 | Porcelain carving material and its preparation method and application |
| CN103804741A (en) * | 2014-01-10 | 2014-05-21 | 芜湖新磊塑胶科技有限公司 | Ceramic sculpture material as well as preparation method and application thereof |
| CN104476788A (en) * | 2014-12-05 | 2015-04-01 | 黑龙江安瑞佳新材料科技开发有限公司 | Glass fiber reinforced polypropylene pipe production device and glass fiber reinforced polypropylene pipe production process |
| WO2016201621A1 (en) * | 2015-06-16 | 2016-12-22 | Borouge Compounding Shanghai Co., Ltd. | Polypropylene composition for pipe applications |
| CN105179824A (en) * | 2015-11-04 | 2015-12-23 | 南京晟林再生资源有限公司 | High-strength wear resistant plastic pipe |
| CN106751354A (en) * | 2016-12-31 | 2017-05-31 | 天津科彩塑料科技有限公司 | A kind of core layer material and preparation method thereof |
| CN109370053A (en) * | 2018-10-24 | 2019-02-22 | 江苏亿超工程塑料有限公司 | A kind of high rigidity polypropylene paper core pipe and preparation method thereof |
| CN110014696A (en) * | 2019-03-01 | 2019-07-16 | 日丰企业集团有限公司 | PA tube of high-strength anti-flaming and preparation method thereof |
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