CN102229723A - Application of polymer additive M4228 in preparing copolypropylene tubing - Google Patents
Application of polymer additive M4228 in preparing copolypropylene tubing Download PDFInfo
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- CN102229723A CN102229723A CN 201110185496 CN201110185496A CN102229723A CN 102229723 A CN102229723 A CN 102229723A CN 201110185496 CN201110185496 CN 201110185496 CN 201110185496 A CN201110185496 A CN 201110185496A CN 102229723 A CN102229723 A CN 102229723A
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Abstract
The invention discloses an application of a polymer additive M4228 in preparing copolypropylene tubing. A dosage of the additive accounts for 0.5% to 1% of the mass of foundation powder of the copolypropylene tubing. The copolypropylene tubing prepared through a method provided in the invention can satisfy mechanical performances required by tubing, bear a comparative inner static pressure, has a good dimensional stability under the pressure, and has a substantially improved service life. In long-term hydraulic strength testing, the service life of the tubing prepared through adding the M4228 is far beyond 50 years in nominal bore at a temperature of 20 DEG C; an oxidation induction period of the tubing prepared by adding the M4228 is more than 80 min; and the hygienic property is improved. The additive M4228 self is nontoxic and odorless, does not influence the product appearance after being added into the tubing, allows the product to have no peculiar smell, and does not get into water to influence the quality of water because the additive M4228 has a good water extraction resistance.
Description
Technical field
The present invention relates to chemical field and material field, specifically is the application of a kind of polymeric additive M4228 on preparation Co-polypropylene tubing.
Background technology
Co-polypropylene tubing is to adopt propylene and two kinds of monomer copolymerizations of ethene to form, and according to the difference of polymerization methods, is divided into atactic copolymerized polypropene (PPR) and block copolymerization polypropylene (PPB) two classes.Two kinds of Co-polypropylene have different thermomechanical properties and roughly similar normal temperature mechanical property.In the production process of whole tube material, the production process of two kinds of polypropylene materials all comprises chemosynthesis and extrudes two parts.The difference of two kinds of tube materials depends primarily on the difference of chemosynthesis process.
The tubing of polypropylene material production has in light weight, and non-scaling is corrosion-resistant, easily processing, advantages such as good heat insulating.Though common polypropylene pipe can satisfy above advantage, also exist not enough: thermal expansivity is bigger when high temperature, and notched Izod impact strength is not high.Because in the life-time service process of polypropylene tube material, what current continued washes away, and especially in the middle of used to make hot water pipe, also will be in for a long time under the environment of comparatively high temps.So polypropylene pipe also must satisfy except that above-mentioned advantage: 1. have favorable mechanical performance and creep-resistant property, guarantee that tubing can bear good dimensional stability under suitable interior static pressure and the pressure; 2. have good sanitation performance, the small-molecule substance in the tube material, because the washing away for a long time down of current, have the phenomenon that certain extracting is separated out, it is as far as possible little to guarantee that small molecules in the material is separated out material, and human body is had no adverse effects; 3. long service life must guarantee that the work-ing life of tubing is more than 50 years.And present PPR and PPB tubing can't satisfy above-mentioned requirements mostly fully.
Summary of the invention
The object of the invention is to provide a kind of polymeric additive M4228 and uses thereof, and especially polymeric additive M4228 is in the application that improves on the polypropylene pipe wood property energy.Purpose of the present invention is achieved by the following technical programs:
The application of a kind of polymeric additive M4228 on preparation Co-polypropylene tubing, comprise behind polymeric additive M4228 and the Co-polypropylene tubing basic powder material mixing, technology joins twin screw extruder routinely, with the 30-40 ton/hour extruded velocity extrude, obtain containing the Co-polypropylene tubing of polymeric additive M4228; It is characterized in that described polymeric additive M4228 is made up of following component by mass percentage:
Preferred version, described polymeric additive M4228 is made up of the following component of mass percent meter:
The preparation method of described polymeric additive M4228 is: after each feed composition of additive mixes stirring 30min in proportion, under the nitrogen protection, 1 normal atmosphere, 180 ℃ of heating, make each component under molten state, stir 30min, the back is pulverized in resulting product cooling cross 200 mesh sieves, collect undersized part and obtain polymeric additive M4228 of the present invention;
The weight-average molecular weight M of described random copolymerization polypropylene pipe basis powder
WBe 596000, molecular weight distribution M
W/ M
N=4.8, ethylene content is 3.2% of a random copolymerization polypropylene pipe basis powder quality;
The weight-average molecular weight M of described Polypropylene Of Raised Temperature Resistance Pipe material basis powder
WBe 519000, molecular weight distribution M
W/ M
N=4.8, ethylene content is 16.3% of a random copolymerization polypropylene pipe basis powder quality;
The quality of described polymeric additive M4228 is the 0.5%-1% of Co-polypropylene tubing basic powder material quality; The quality of preferred polymers additive M4228 is 0.7% of a Co-polypropylene tubing basic powder material quality.
Described 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is the polynary Hinered phenols antioxidant of high molecular, have good heat resistance, do not pollute, not painted, characteristics such as volatility is low, produce by Ciba company limited, skeleton symbol is as follows:
Described 3-(1, the 1-dimethyl ethyl)-β-[3-(1, the 1-dimethyl ethyl)-the 4-hydroxyphenyl]-4-hydroxy-beta-tolyl acid-ethylene ester, belong to high-efficient phenol antioxidant, available oxygen content height, the high resistance hydrolysis provides long term thermal stable to polyolefine, is specially adapted to touch the plastics of water, wet goods spe medium, produced by Clariant chemical industry company limited, skeleton symbol is as follows:
Described 3,9-two (2,4-dicumyl phenoxy group)-2; 4,8,10-four oxa-s-3; 9-two phospha spiral shell [5.5] undecanes are high molecular, low volatilization; the phosphite oxidation inhibitor of high content of phosphorus (7.3%); molecular weight 852, fusing point have the low volatility under excellent high-temperature stability and the high temperature and remarkable anti-xanthochromia is arranged and the high temperature degradation protection in the courses of processing greater than 225 ℃; produced by Dover chemical company, skeleton symbol is as follows:
Described DHT-4A is artificial synthetic hydrotalcite, and as acid neutralizing agent, Japan consonance chemical industrial company produces in manufacture of polyolefins;
Described polyethylene wax PE 520 can be used for adjusting polyolefinic flowability, and does not influence mechanical property, has good thermostability, can improve the surface lubrication of finished product, and molecular-weight average is approximately 2300, and Clariant chemical industry company limited produces.
Co-polypropylene tubing of the present invention adopts the known conventional preparation method of those skilled in the art to finish, involved concrete grammar and parameter, and the present invention does not do and gives unnecessary details; Inventive point of the present invention is the component of polymeric additive M4228 and the proportioning of this additive and copolymerization polypropylene pipe basis powder.
Beneficial effect of the present invention is: the Co-polypropylene tubing that the inventive method obtains, (1) satisfy the desired mechanical property of tubing and bear good dimensional stability under suitable interior static pressure and the pressure, and be significantly improved work-ing life.In the long-term hydrostatic strength test, add tubing that M4228 produces 50 years head and shoulders above work-ing life of 20 ℃ under nominal pipe size; The oxidation induction period of the tubing that interpolation M4228 makes is more than 80min, and the oxidation induction period of general tubing is about 40min.(2) sanitation performance improves, the nontoxic odorlessness of additive M4228 itself, in adding tube material after, can not influence the outward appearance of product, can not make product have peculiar smell yet, because its water-fast extracting performance is good,, influence water quality in addition so also can not enter into water.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The preparation of polymeric additive M4228:
1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is 35 parts; 3-(1, the 1-dimethyl ethyl)-β-[3-(1, the 1-dimethyl ethyl)-4-hydroxyphenyl]-4-hydroxy-beta-tolyl acid-ethylene ester is 30 parts; 3,9-two (2,4-dicumyl phenoxy group)-2,4,8,10-four oxa-s-3,9-two phospha spiral shell [5.5] undecanes are 20 parts; DHT-4A is 10 parts; Polyethylene wax is 5 parts; Behind above-mentioned each component mixing stirring 30min; under the nitrogen protection, 1 normal atmosphere, 180 ℃ of heating make each component stir 30min under molten state; the back is pulverized in resulting product cooling cross 200 mesh sieves, collect undersized part and obtain polymeric additive M4228 of the present invention.
Embodiment 2
With random copolymerization tubing basis powder (weight-average molecular weight M
W: 596000, molecular weight distribution (M
W/ M
N)=4.8, ethylene content (wt%): 3.2) and polymeric additive M4228 (prepared) by embodiment 1 by 100: 0.7 quality than thorough mixing after, add twin screw extruder, extrude with the extruded velocity of 30-40 ton/h.The screw zones temperature of reaction is 200 ℃, 220 ℃, and 230 ℃, 250 ℃, 270 ℃, 270 ℃, 270 ℃, 260 ℃, 250 ℃, 230 ℃.
Embodiment 3
With block copolymerization tubing basis powder (weight-average molecular weight M
W: 519000, molecular weight distribution (M
W/ M
N)=4.8, ethylene content (wt%): 16.3) and polymeric additive M4228 (prepared) by embodiment 1 by 100: 0.7 quality than thorough mixing after, add twin screw extruder, extrude with the extruded velocity of 30-40 ton/h.The screw zones temperature of reaction is 200 ℃, 220 ℃, and 230 ℃, 250 ℃, 270 ℃, 270 ℃, 270 ℃, 260 ℃, 250 ℃, 230 ℃.
It is as shown in the table that the tube material that embodiment 2,3 is produced carries out the test of mechanical property:
The contrast of the mechanical property of table 1 embodiment 2,3 and contrast sample
Annotate: contrast sample 1 is the C4220 tube material, and contrast sample 2 is the B8101 tube material.
From above table as can be seen, still be the hot workability aspect no matter from mechanical property, the polypropylene tube material product that uses this polymeric additive M4228 to produce all satisfies the tubing processing needs in current market fully.
Embodiment 4 carries out prediction of strength with the polypropylene pipe that embodiment 2 produces
Institute's sample product are estimated according to standard GB/T18252-2008 " plastic duct system; determine the long-term hydrostatic intensity of thermoplastic material with the tubing form with extrapotation ", 20 ℃, 50 years, the long-term hydrostatic intensity σ of tubing of 97.5% confidence lower limit
LPLBe 10.82MPa, the minimum desired strength MRS=10.0MPa of respective material.Illustrate the tubing produced with polymeric additive M4228 50 years head and shoulders above work-ing life of 20 ℃ under nominal pipe size to have favorable mechanical performance and creep-resistant property, meet the requirement of supplying pipe.Can guarantee that tubing bears good dimensional stability under suitable interior static pressure and the pressure.
Table 2 is pressed the prediction of strength of the polypropylene pipe of embodiment 2 productions
| Temperature/℃ | Time/year | σ LTHS/MPa | σ LPL/MPa |
| 20 | 50.00 | 11.36 | 10.82 |
| 20 | 100.00 | 10.50 | 9.39 |
| 70 | 50.00 | 3.22 | 2.99 |
| 95 | 4.06 | 2.77 | 2.61 |
| 110 | 1.02 | 2.56 | 2.42 |
Embodiment 5 oxidation induction periods are measured
Used instrument: differential scanning calorimeter (DSC), Pyris 1 DSC, U.S. Perkin Elmer company produces.200 ℃ of probe temperatures, ASTM D3895-07 is followed in test.
Measure the oxidation induction period that embodiment 2 makes product.With three kinds of schemes sample is handled respectively, tested the oxidation induction period of sample under each environment.
Scheme 1: the oxidation induction period of normal each sample of test sample.This oxidation induction period characterizes each sample when placing in the ordinary course of things, the ageing-resistant degree of material.
Scheme 2: place 20 ℃ circulation flowing water (water flow velocity is set at 5m/s) after 720 hours in each sample, test its oxidation induction period, this oxidation induction period exosyndrome material under the washing away of long-term cold water flow, the ageing-resistant degree of material.
Scheme 3: place 90 ℃ circulation flowing water (water flow velocity is set at 5m/s) after 240 hours in each sample, test its oxidation induction period, this oxidation induction period exosyndrome material under the washing away of long term thermal current, the ageing-resistant degree of material.
The mean value of test gained is as follows:
Table 3 embodiment 2 makes the mensuration (unit: min) of product oxidation induction period (OIT)
From The above results as can be known, the oxidation induction period of this product all more than 80min, illustrates that this tube material has stability preferably, satisfies the requirement of the tube material of long-term contact tap water.
Claims (3)
1. the application of polymeric additive M4228 on preparation Co-polypropylene tubing comprises the step with polymeric additive M4228 and Co-polypropylene tubing basic powder material mixing; It is characterized in that described polymeric additive M4228 is made up of following component by mass percentage:
The quality of described additive M4228 is the 0.5%-1% of Co-polypropylene tubing basic powder material quality;
Described Co-polypropylene tubing basic powder material is random copolymerization polypropylene pipe basis powder or Polypropylene Of Raised Temperature Resistance Pipe material basis powder;
The weight-average molecular weight M of described random copolymerization polypropylene pipe basis powder
WBe 596000, molecular weight distribution M
W/ M
N=4.8, ethylene content is 3.2% of a random copolymerization polypropylene pipe basis powder quality;
The weight-average molecular weight M of described Polypropylene Of Raised Temperature Resistance Pipe material basis powder
WBe 519000, molecular weight distribution M
W/ M
N=4.8, ethylene content is 16.3% of a Polypropylene Of Raised Temperature Resistance Pipe material basis powder quality.
2. the application of polymeric additive M4228 according to claim 1 on preparation Co-polypropylene tubing is characterized in that described polymeric additive M4228 is made up of following component by mass percentage:
3. the application on preparation Co-polypropylene tubing according to claim 1 or 2 described polymeric additive M4228, the quality that it is characterized in that described additive M4228 is 0.7% of a Co-polypropylene tubing basic powder material quality.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110185496A CN102229723B (en) | 2011-07-04 | 2011-07-04 | Application of polymer additive M4228 in preparing copolypropylene tubing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110185496A CN102229723B (en) | 2011-07-04 | 2011-07-04 | Application of polymer additive M4228 in preparing copolypropylene tubing |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634119A (en) * | 2012-04-19 | 2012-08-15 | 大连兴辉化工有限公司 | Special assistant SYNOX M4229 for beta-crystal-form random copolymerization polypropylene tube materials and application thereof |
| EP3421529A1 (en) * | 2017-06-29 | 2019-01-02 | Songwon Industrial Co., Ltd. | Polyolefin articles with improved resistance against chlorine dioxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010000638A1 (en) * | 2008-07-02 | 2010-01-07 | Basf Se | Blends of stabilizers for aliphatic polyesters |
| CN101759922A (en) * | 2008-12-26 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Light aging resistant polypropylene composition and preparation method thereof |
-
2011
- 2011-07-04 CN CN201110185496A patent/CN102229723B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010000638A1 (en) * | 2008-07-02 | 2010-01-07 | Basf Se | Blends of stabilizers for aliphatic polyesters |
| CN101759922A (en) * | 2008-12-26 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Light aging resistant polypropylene composition and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634119A (en) * | 2012-04-19 | 2012-08-15 | 大连兴辉化工有限公司 | Special assistant SYNOX M4229 for beta-crystal-form random copolymerization polypropylene tube materials and application thereof |
| EP3421529A1 (en) * | 2017-06-29 | 2019-01-02 | Songwon Industrial Co., Ltd. | Polyolefin articles with improved resistance against chlorine dioxide |
| WO2019003065A1 (en) | 2017-06-29 | 2019-01-03 | Songwon Industrial Co., Ltd. | Polyolefin articles with improved resistance against chlorine dioxide |
| CN110770260A (en) * | 2017-06-29 | 2020-02-07 | 松原产业株式会社 | Polyolefin articles having improved resistance to chlorine dioxide |
| JP2020525556A (en) * | 2017-06-29 | 2020-08-27 | ソンウォン インダストリアル カンパニー リミテッドＳｏｎｇｗｏｎ Ｉｎｄｕｓｔｒｉａｌ Ｃｏ．， Ｌｔｄ． | Polyolefin article with improved resistance to chlorine dioxide |
| EP3645583A4 (en) * | 2017-06-29 | 2021-04-28 | Songwon Industrial Co., Ltd. | Polyolefin articles with improved resistance against chlorine dioxide |
| JP7160822B2 (en) | 2017-06-29 | 2022-10-25 | ソンウォン インダストリアル カンパニー リミテッド | Polyolefin article with improved resistance to chlorine dioxide |
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| CN102229723B (en) | 2012-10-24 |
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