CN102229723B - Application of polymer additive M4228 in preparing copolypropylene tubing - Google Patents

Application of polymer additive M4228 in preparing copolypropylene tubing Download PDF

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Publication number
CN102229723B
CN102229723B CN201110185496A CN201110185496A CN102229723B CN 102229723 B CN102229723 B CN 102229723B CN 201110185496 A CN201110185496 A CN 201110185496A CN 201110185496 A CN201110185496 A CN 201110185496A CN 102229723 B CN102229723 B CN 102229723B
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tubing
additive
copolypropylene
copp
quality
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CN102229723A (en
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任国辉
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DALIAN XINGHUI CHEMICAL CO LTD
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DALIAN XINGHUI CHEMICAL CO LTD
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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

The application of polymeric additive M4228 on preparation COPP tubing
Technical field
The present invention relates to chemical field and field of materials, specifically is the application of a kind of polymeric additive M4228 on preparation COPP tubing.
Background technology
COPP tubing is to adopt propylene and two kinds of monomer copolymerizations of ethene to form, and the difference according to polymerization methods is divided into two types of atactic copolymerized polypropene (PPR) and block copolymerization polypropylenes (PPB).Two kinds of COPPs 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, is prone to 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 PA 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, the work-ing life that must guarantee 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 ability.The object of the invention is achieved through following technical scheme:
The application of a kind of polymeric additive M4228 on preparation COPP tubing; Comprise behind polymeric additive M4228 and the COPP tubing basic powder material mixing; Join twin screw extruder by common process; With the 30-40 ton/hour extruded velocity extrude, obtain containing the COPP tubing of polymeric additive M4228; It is characterized in that said polymeric additive M4228 is made up of following component by mass percentage:
Preferred version, said polymeric additive M4228 is made up of the following component of mass percent meter:
The preparation method of said 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 according to the invention;
The weight-average molecular weight M of said random copolymerization polypropylene pipe basis powder WBe 596000, MWD 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 said Polypropylene Of Raised Temperature Resistance Pipe material basis powder WBe 519000, MWD M W/ M N=4.8, ethylene content is 16.3% of a random copolymerization polypropylene pipe basis powder quality;
The quality of said polymeric additive M4228 is the 0.5%-1% of COPP tubing basic powder material quality; The quality of preferred polymers additive M4228 is 0.7% of a COPP tubing basic powder material quality.
Said 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 HMW; Have good heat resistance, do not pollute, not painted, characteristics such as volatility is low, produce by Ciba ltd, skeleton symbol is following:
Said 3-(1, the 1-dimethyl ethyl)-β-[3-(1, the 1-dimethyl ethyl)-4-phenylor]-4-hydroxy-beta-tolyl acid-1; 2-ethylidene ester belongs to high-efficient phenol antioxidant, and available oxygen content is high; 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 ltd, skeleton symbol is following:
Said 3,9-two (2,4-dicumyl phenoxy)-2,4; 8,10-four oxa-s-3,9-two phospha spiral shell [5.5] undecanes are HMWs; Low volatilization, the phosphite oxidation inhibitor of high content of phosphorus (7.3%), molecular weight 852, fusing point is greater than 225 ℃; 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 course of processing, produced by Dover chemical company, skeleton symbol is following:
Said DHT-4A is artificial synthetic hydrotalcite, and as acid neutralizing agent, Japan consonance chemical industrial company produces in manufacture of polyolefins;
Said 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 property of finished product, and molecular-weight average is approximately 2300, and Clariant chemical industry ltd produces.
COPP tubing according to the invention adopts the known conventional preparation method of those skilled in the art to accomplish, 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 COPP 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 is further specified.
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-phenylor]-4-hydroxy-beta-tolyl acid-ethylene ester is 30 parts; 3,9-two (2,4-dicumyl phenoxy)-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 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 according to the invention.
Embodiment 2
With random copolymerization tubing basis powder (weight-average molecular weight M W: 596000, MWD (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, MWD (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 comparison sample
Annotate: comparison sample 1 is the C4220 tube material, and comparison sample 2 is the B8101 tube material.
No matter can find out from above table, still be that the hot workability aspect is seen from mechanical property, and the PA 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 article are estimated according to standard GB/T18252-2008 " plastic duct system; confirm that with extrapotation thermoplastic material is with the hydrostatic intensity of tubing forms of chronic ", 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.Explain 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: DSC (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.When this each sample of oxidation induction period sign is placed 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 MV of test gained is following:
Table 3 embodiment 2 makes the mensuration (unit: min) of product oxidation induction period (OIT)
Can know that from The above results the oxidation induction period of this product all more than 80min, explains 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 COPP tubing comprises the step with polymeric additive M4228 and COPP tubing basic powder material mixing; It is characterized in that said polymeric additive M4228 is made up of following component by mass percentage:
The quality of said additive M4228 is the 0.5%-1% of COPP tubing basic powder material quality;
Said COPP 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 said random copolymerization polypropylene pipe basis powder WBe 596000, MWD 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 said Polypropylene Of Raised Temperature Resistance Pipe material basis powder WBe 519000, MWD 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 COPP tubing is characterized in that said polymeric additive M4228 is made up of following component by mass percentage:
3. according to claim 1 or the application of 2 said polymeric additive M4228 on preparation COPP tubing, the quality that it is characterized in that said additive M4228 is 0.7% of a COPP tubing basic powder material quality.
CN201110185496A 2011-07-04 2011-07-04 Application of polymer additive M4228 in preparing copolypropylene tubing Active CN102229723B (en)

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CN102634119B (en) * 2012-04-19 2014-03-26 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

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Publication number Priority date Publication date Assignee Title
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

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CN102137890A (en) * 2008-07-02 2011-07-27 巴斯夫欧洲公司 Blends of stabilizers for aliphatic polyesters

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Publication number Priority date Publication date Assignee Title
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

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