CN106554448B - High-impact transparent polypropylene resin - Google Patents
High-impact transparent polypropylene resin Download PDFInfo
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- CN106554448B CN106554448B CN201510640822.0A CN201510640822A CN106554448B CN 106554448 B CN106554448 B CN 106554448B CN 201510640822 A CN201510640822 A CN 201510640822A CN 106554448 B CN106554448 B CN 106554448B
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Abstract
The invention belongs to polymeric material fields, and in particular to a kind of high-impact transparent polypropylene resin.High-impact transparent polypropylene resin includes random impact polypropylene resin, the random impact polypropylene resin is that propylene monomer and vinyl monomer polymerization obtain, wherein the weight content of vinyl monomer is in 4.0-8.0%, 1-3% takes part in random copolymerization reaction and forms atactic copolymerized polypropene, and 3-5% takes part in crushing-resistant copolymerization reaction and forms impact copolymer polypropylene.The transparent anti-impact good combination property of high-impact transparent polypropylene resin of the present invention, application cost is low, rigidity is high, processing viscosity is low, easily molded.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of high-impact transparent polypropylene resin.
Background technique
Acrylic resin has good heat resistance, processability and mechanical strength, at the same also have density is low, Yi Huishou,
The features such as can be recycled is widely used in the fields such as automobile, electric appliance, daily necessities, household and packaging.Transparent polypropylene is due to system
Product it is transparent it is beautiful, wholesomeness is good, heat-resisting, price is low etc., food packaging, medical article, media product packaging, finishing box and
Beverage bottle, feeding bottle etc. are widely applied.Just because of many advantages of transparent polypropylene, come out from last century early eighties
Since, it is developed rapidly in the whole world.China's transparent polypropylene consumption figure also increases rapidly, by China in 2012 transparent poly- third
Alkene consumption figure has reached 600,000 tons/year.
Conventional transparent polypropylene is usually to obtain after adding clarifier in homopolymerization or atactic copolymerized polypropene, is existed at present
More prominent problem present in use is that the impact property under impact property especially low-temperature condition is low, and being unable to satisfy makes
With requiring.And impact polypropylene, due to introducing rubber phase in polypropylene matrix, normal low-temperature impact resistance greatly improves, but
Its transparency is poor, and mist degree generally 60% or so, is unable to satisfy demand of the numerous areas to the transparency.
In the case where not only needing the transparency to need high impact properties again, it is main at present using by random polypropylene and POP,
POE, SEBS etc. elastomer blended method, this method can be improved the impact resistance of material to a certain extent, but also band
Carry out many adverse effects, such as: the elastomer price of addition is high and needs to be granulated by twin-screw, production cost can be made to have larger
Increase, while elastomer-modified product can be such that mist degree increases, rigidity declines, processing viscosity increases, and leverage product
The transparency, rigidity simultaneously increase difficulty of processing, process-cycle extension, and the introducing of elastomer also declines the wholesomeness of material,
The application in the fields such as medical treatment, food packaging is restricted.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of high-impact transparent polypropylene resins, transparent anti-
Rush good combination property, application cost are low, rigidity is high, processing viscosity it is low, easily molded.
High-impact transparent polypropylene resin of the present invention, including random impact polypropylene resin, the random anti-impact are poly-
Allyl resin is that propylene monomer and vinyl monomer polymerization obtain, and wherein the weight content of vinyl monomer is in 4.0-8.0%, 1-
3%, which takes part in random copolymerization reaction, forms atactic copolymerized polypropene, and 3-5% takes part in crushing-resistant copolymerization reaction, and to form anti-impact total
Poly- polypropylene.
Wherein:
Random impact polypropylene resin of the present invention is that propylene monomer and vinyl monomer polymerization obtain, wherein ethylene
The weight content of monomer takes part in random copolymerization reaction in 4.0-8.0%, preferably 4.0-6.0%, 1-3% therein and forms nothing
Copolymer polypropylene is advised, 3-5% takes part in crushing-resistant copolymerization reaction and forms impact copolymer polypropylene.Atactic copolymerized polypropene part pair
Improving the transparency of product and increasing homopolymerization part and the compatibility of anti-impact part has positive effect, impact copolymer polypropylene part
Decisive role is played to the impact resilience for improving product, compared with common impact polypropylene, crushing-resistant copolymerization part contains in the resin
It measures less, good dispersion, can effectively absorb impact energy blocks the crackle caused, while greatly improving impact resilience, to saturating
Bright property will not adversely affect.Due to the above design feature, resin of the present invention is made to be provided simultaneously with high-impact and high transparency
The characteristics of.
Random impact polypropylene resin is propylene monomer and vinyl monomer preferably under the action of ziegler natta catalyst
What polymerization obtained, but it is also not necessarily limited to such catalyst preparation.
The present invention is that the random impact polypropylene resin M FR is 1-30g/10min, preferably 8-20g/10min.
Random impact polypropylene resin mist degree≤13% of 1mm thickness thin slice, simply supported beam notch impact strength >=13kJ/
m2。
As a preference, random impact polypropylene resin of the present invention the preparation method is as follows:
1) propylene and hydrogen are passed through in two annular-pipe reactors, polymerization generates homopolypropylene；
2) product enters gas phase kettle and is passed through ethylene in gas phase kettle, forms ethylene-propylene copolymer.
Wherein: the concentration of hydrogen is 100-2000 × 10 in the first endless tube-6, remaining is propylene；Hydrogen in second endless tube
Concentration be 100-2000 × 10-6, remaining is propylene.Gas phase kettle pressure is 0.1-2.0MPa, and gas phase kettle temperature degree is 70-80
DEG C, the molar ratio (C=of the sum of ethylene and ethylene and propylene in gas phase kettle2/ C=2+ C=3It (mol/mol)) is 0.01-0.5, gas
Volume ratio (the H of the sum of hydrogen and ethylene and propylene in phase kettle2/ C=2+ C=3It (v/v)) is 0.01-0.1.
High-impact transparent polypropylene resin of the present invention, the raw material including following parts by weight:
Random impact polypropylene resin, clarifier 2000-4000ppm, antioxidant 1000-3000ppm, lubricant 200-
800ppm, acid absorbent 500-1000ppm.
Wherein:
Clarifier is phosphoric acid salt or glucitols clarifier, and but it is not limited to this, dosage 2000-4000ppm,
That is clarifier accounts for the 2000-4000ppm of all raw material total amounts, preferably 2800-3500ppm.
Antioxidant is one or both of Hinered phenols antioxidant or phosphite antioxidant, commercial product, dosage
1000-3000ppm, preferably 2000ppm.Antioxidant is preferably the compound of antioxidant 1010 and 168, and the two compounding weight ratio is
1:1。
Acid absorbent is stearate, such as calcium stearate, zinc stearate or odium stearate, the preferred calcium stearate of acid absorbent, contracting
It is written as Cast.
Lubricant is glycerin monostearate, fatty acid metal salts, fatty acid amide or wax；It is preferred that glycerin monostearate,
Its sour glycerine ester of entitled list 18 (alkane) of chemistry, abbreviation monoglyceride GMS.
High-impact transparent polypropylene resin of the present invention can be used for injector for medical purpose, household clear plastic articles, family
Electrical components etc. meet medical apparatus health, food packaging health demand, and can realize the double effects of high transparency high-impact.
All raw materials are carried out melting mixing granulation by the preparation method of high-impact transparent polypropylene resin of the present invention
Preparation.
In conclusion the invention has the following advantages that
(1) present invention includes the random impact polypropylene resin that a kind of propylene monomer and vinyl monomer polymerization obtain, wherein
The weight content of vinyl monomer takes part in random copolymerization reaction in 4.0-8.0%, 1-3% therein and forms random copolymerization poly- third
Alkene, 3-5% take part in crushing-resistant copolymerization reaction and form impact copolymer polypropylene.Atactic copolymerized polypropene part is final to raising to be produced
The transparency of product and the compatibility of increase homopolymerization part and anti-impact part have positive effect, and impact copolymer polypropylene part is to raising
The impact resilience of product plays decisive role, and compared with common impact polypropylene, crushing-resistant copolymerization moiety content is few in the resin, divides
Dissipate that property is good, can effectively absorb impact energy blocks the crackle caused, to while greatly improving impact resilience, will not to the transparency
It adversely affects.Due to the above design feature, the characteristics of making resin of the present invention be provided simultaneously with high-impact and high transparency.
(2) the present invention provides a kind of random impact polypropylene resins, and it is poly- to generate copolymerization by propylene and ethylene copolymerization
Propylene makes resin impact resilience, the transparency reach higher balance including random copolymerization and crushing-resistant copolymerization two kinds of polymer.
The resin can be used for injector for medical purpose, household clear plastic articles, appliances parts etc., solve asking for the easy fragmentation of opaque products
Topic.Compared with the method for adding elastic body toughening in random polypropylene, the resulting acrylic resin transparency of the invention is high, anti-
Punching property is good, simultaneously because not using elastomer, raw material application cost is substantially reduced.
(3) high-impact transparent polypropylene resin of the present invention can be used for injector for medical purpose, household clear plastic articles,
Appliances parts etc. meet medical apparatus health, food packaging health demand, and can realize the double effects of high transparency high-impact,
Compared with the commercial routes for adding elastic body toughening in random transparent polypropylene, resin of the invention is comprehensive with transparent anti-impact
The features such as performance is good, application cost is low, rigidity is high, processing viscosity is low, easily molded.
(4) present invention realizes high balance of the acrylic resin in terms of impact resilience and the transparency.
Detailed description of the invention
Fig. 1 is random impact polypropylene resin, atactic copolymerized polypropene resin and crushing-resistant copolymerization poly- third prepared by the present invention
The spectrogram of olefine resin three.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Converging operation employed in the present invention is the Sphripol polymerization in 70,000 tons of annual bicyclic pipes, single gas phase kettle
It is carried out on device, but can realize that the device of the invention is without being limited thereto.Ziegler natta catalyst is used in embodiment and is given
Electron carries out combined polymerization to gas phase kettle and ethylene after bicyclic pipe Liquid-phase reactor is passed through propylene and hydrogen is polymerize, obtains
The polymer arrived is granulated after mixing with additive metering by double screw extruder, and final high-impact high transparency copolymerization poly- third is obtained
Olefine resin product.
Embodiment 1-4 and comparative example 1-4
Embodiment 1-4 prepares a kind of high-impact transparent polypropylene resin, raw material used be shown in Table 1 used in raw material group
Part and one column of mass fraction；The polymerization technique and technological parameter of random impact polypropylene resin in raw material are shown in Table in 1 and randomly resist
Rush one column of polymerization technique and technological parameter of acrylic resin；The ethylene contents of the random part of random impact polypropylene resin,
The ethylene contents and MFR of anti-impact part are shown in Table one column of parameter of random impact polypropylene resin in 1, and the highly resistance being prepared is punched through
The performance of bright acrylic resin is shown in Table one column of performance of product in 1.
The raw material grade performance characterization etc. of corresponding comparative example 1-4 is shown in Table 2.
Standard used by being tested for the property in embodiment 1-4 and comparative example 1-4 to naval stores and method are as follows:
Melt mass flow rate: it is carried out by GB/T 3682-2000；
Simply supported beam notch impact strength: being tested by GB/T 1043.1-2008, and wherein low-temperature process is -20 DEG C of placements
2 hours, room temperature treatment process was 23 DEG C and places 24 hours；
Mist degree: carrying out according to GB/T 2410-2008, and sample thickness is 1mm when not marking；
Bending elastic modulus, bending stress are carried out by GB/T 9341-2008；
Load deformation temperature is carried out by GB/T 1634.2-2004.
1 embodiment 1-4 of table and its performance characterization
2 comparative example 1-4 of table and its performance characterization
Using infrared spectrometer to random impact polypropylene resin prepared by the present invention and other different types of polypropylene
The characterization for the infrared spectroscopy that resin carries out.It is successively resin of the present invention, atactic copolymerized polypropene resin, crushing-resistant copolymerization from top to bottom
The spectrogram of three kinds of products of acrylic resin.Wherein resin of the invention is in 731cm-1、720cm-1There are obvious absorption peaks in position,
Show that the polymerization that wherein there is random pattern has long ethylene segment i.e. impact copolymer again.Intermediate random copolymerization poly- third
Only in 731cm on alkene spectrogram-1There is apparent absorption peak in position, shows that ethylene, propylene monomer are mainly with random copolymerization in the product
Based on, in 720cm on nethermost crushing-resistant copolymerization product spectrogram-1、730cm-1The absorption of position then shows there is long in product
Ethylene segment, mainly impact copolymer.
Claims (1)
1. a kind of high-impact transparent polypropylene resin, it is characterised in that: including random impact polypropylene resin, the random anti-impact is poly-
Allyl resin is that propylene monomer and vinyl monomer polymerization obtain, and wherein the weight content of vinyl monomer is 5.27%, and 3% takes part in
Random copolymerization reaction forms atactic copolymerized polypropene, and 2.27%, which takes part in crushing-resistant copolymerization reaction, forms impact copolymer polypropylene；
The random impact polypropylene resin is that propylene monomer and vinyl monomer polymerize under the action of ziegler natta catalyst
It obtains；
The high-impact transparent polypropylene resin includes the raw material of following mass fraction: random 99.42 parts of impact polypropylene resin,
0.3 part of Sorbitol Nucleator, 0.1 part of antioxidant 1010,0.05 part of irgasfos 168,0.05 part of acid absorbent calcium stearate, profit
0.08 part of lubrication prescription GMS；
The random impact polypropylene resin the preparation method is as follows:
1) propylene and hydrogen are passed through in two annular-pipe reactors, polymerization generates homopolypropylene；
2) product enters gas phase kettle and is passed through ethylene in gas phase kettle, forms ethylene-propylene copolymer；
Wherein: the concentration of hydrogen is 1901 × 10 in the first endless tube-6, remaining is propylene；The concentration of hydrogen is in second endless tube
1660×10-6, remaining is propylene；Gas phase kettle pressure is 1.3MPa, and gas phase kettle temperature degree is 78 DEG C, ethylene and ethylene in gas phase kettle
It is 0.11 with the molar ratio of the sum of propylene, the volume ratio of the sum of hydrogen and ethylene and propylene is 0.05 in gas phase kettle.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107245194B (en) * | 2017-04-14 | 2021-02-26 | 中国石油化工股份有限公司 | Preparation method of high-strength heat-resistant random copolymerization polypropylene resin |
| CN109627596B (en) * | 2017-10-09 | 2021-10-22 | 中国石油化工股份有限公司 | Polypropylene master batch with haze increasing effect, preparation method and application thereof |
| CN107880402A (en) * | 2017-11-23 | 2018-04-06 | 上海帆顺包装集团有限公司 | It is adapted to the high transparency high impact resistance polypropylene resin of blow molding process |
| CN110256619B (en) * | 2019-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Polypropylene polymer, preparation method and high-gloss polypropylene resin prepared from polypropylene polymer |
| CN112759692A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Production method of haze-adjustable impact-resistant polypropylene cast film |
| CN114058113B (en) * | 2020-08-10 | 2023-09-26 | 中国石油天然气股份有限公司 | High-impact transparent polypropylene resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045983A (en) * | 1988-12-14 | 1990-10-10 | 希蒙特公司 | Have good transparency and improved the prolylene polymer composition of shock strength |
| JP2000191861A (en) * | 1998-10-20 | 2000-07-11 | Mitsui Chemicals Inc | Soft polypropylene composition |
| CN103030886B (en) * | 2012-12-20 | 2014-11-26 | 中国石油天然气股份有限公司 | Transparent polypropylene and preparation method thereof |
| CN104448537A (en) * | 2013-09-18 | 2015-03-25 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof and products made from polypropylene composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0725849B2 (en) * | 1988-02-04 | 1995-03-22 | 三井東圧化学株式会社 | Method for producing propylene-ethylene copolymer |
-
2015
- 2015-09-30 CN CN201510640822.0A patent/CN106554448B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045983A (en) * | 1988-12-14 | 1990-10-10 | 希蒙特公司 | Have good transparency and improved the prolylene polymer composition of shock strength |
| JP2000191861A (en) * | 1998-10-20 | 2000-07-11 | Mitsui Chemicals Inc | Soft polypropylene composition |
| CN103030886B (en) * | 2012-12-20 | 2014-11-26 | 中国石油天然气股份有限公司 | Transparent polypropylene and preparation method thereof |
| CN104448537A (en) * | 2013-09-18 | 2015-03-25 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof and products made from polypropylene composition |
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