CN106554448A - High-impact transparent polypropylene resin - Google Patents
High-impact transparent polypropylene resin Download PDFInfo
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- CN106554448A CN106554448A CN201510640822.0A CN201510640822A CN106554448A CN 106554448 A CN106554448 A CN 106554448A CN 201510640822 A CN201510640822 A CN 201510640822A CN 106554448 A CN106554448 A CN 106554448A
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Abstract
The invention belongs to polymeric material field, 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 are obtained, wherein the weight content of vinyl monomer is in 4.0-8.0%, 1-3% take part in random copolymerization reaction and define atactic copolymerized polypropene, and 3-5% take part in crushing-resistant copolymerization reaction and define 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, easy-formation.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of high-impact transparent polypropylene resin.
Background technology
Acrylic resin has good thermostability, processability and mechanical strength, at the same also have that density is low, easy recovery,
The features such as can be recycled, is widely used in the fields such as automobile, electrical equipment, article of everyday use, household and packaging.Transparent polypropylene
As the transparent attractive in appearance, wholesomeness of product is good, heat-resisting, price is low, in packaging for foodstuff, medical article, media product bag
The extensively application of the aspect such as dress, box and carafe, feeding bottle.Just because of many advantages of transparent polypropylene, from upper
Since century early eighties appearance, it has been developed in the whole world rapidly.China's transparent polypropylene consumption figure is also increased rapidly,
600,000 tons/year have been reached by China's transparent polypropylene consumption figure in 2012.
What conventional transparent polypropylene was obtained after being typically to add clarifier in homopolymerization or atactic copolymerized polypropene, make at present
The more prominent problem with present in is, impact property of its impact property especially under low temperature state is low, it is impossible to which satisfaction makes
With requiring.And impact polypropylene, due to introducing rubber phase in polypropylene matrix, normal low-temperature impact resistance is greatly improved,
But its transparency is poor, and mist degree is typically 60% or so, it is impossible to meet demand of the numerous areas to the transparency.
Not only needing the transparency and in the case of needing high impact properties, it is main at present using by random polypropylene and POP,
POE, SEBS etc. elastomer blended method, this method can improve the impact resistance of material to a certain extent,
But many adverse effects are also brought, such as：The elastomer price of addition is high, and need, through twin screw pelletize, to make production
Cost has a larger increase, while elastomer-modified product increases can mist degree, rigidity declines, processing viscosity increases, greatly
Have impact on greatly product it is transparent, rigid, and increased difficulty of processing, process-cycle and extend, the introducing of elastomer also makes
The wholesomeness of material declines, and the application in fields such as medical treatment, packagings for foodstuff is restricted.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of high-impact transparent polypropylene resin, transparent anti-impact synthesis
Performance is good, application cost is low, rigidity is high, processing viscosity is low, easy-formation.
High-impact transparent polypropylene resin of the present invention, including random impact polypropylene resin, the random impact polypropylene tree
Fat is that propylene monomer and vinyl monomer polymerization are obtained, and in 4.0-8.0%, 1-3% take part in nothing to the wherein weight content of vinyl monomer
Rule copolyreaction defines atactic copolymerized polypropene, and 3-5% take part in crushing-resistant copolymerization reaction and define impact copolymer polypropylene.
Wherein：
Random impact polypropylene resin of the present invention is what propylene monomer and vinyl monomer polymerization were obtained, wherein vinyl monomer
In 4.0-8.0%, preferred 4.0-6.0%, 1-3% therein take part in random copolymerization reaction and define atactic copolymerized polypropene weight content,
3-5% take part in crushing-resistant copolymerization reaction and define impact copolymer polypropylene.The transparency of the atactic copolymerized polypropene part to raising product
There are positive role, impact resilience of the impact copolymer polypropylene part to raising product with the compatibility of the homopolymerization part with anti-impact part is increased
Decisive role is played, compared with common impact polypropylene, in the resin crushing-resistant copolymerization moiety content is few, good dispersion, can
Effectively absorbing impact energy blocks the crackle of initiation, while impact resilience is greatly improved, does not result in adverse effect to the transparency.
Due to above construction featuress, the characteristics of make resin of the present invention be provided simultaneously with high-impact and high transparency.
Acquisition that random impact polypropylene resin is propylene monomer and vinyl monomer is polymerized preferably in the presence of ziegler natta catalyst
, but it is also not necessarily limited to this kind of catalyst preparation.
It is 1-30g/10min, preferably 8-20g/10min that the present invention is described random impact polypropylene resin M FR.
Random impact polypropylene resin mist degree≤13% of 1mm thickness thin slices, simply supported beam notch impact strength >=13kJ/m2。
As one kind preferably, the preparation method of random impact polypropylene resin of the present invention is as follows：
1) propylene and hydrogen are passed through in two annular-pipe reactors, are polymerized and generate HOPP；
2) product is passed through ethylene into gas phase kettle and in gas phase kettle, forms ethylene-propylene copolymer.
Wherein：In first endless tube, the concentration of hydrogen is 100-2000 × 10-6, it is remaining for propylene；The concentration of hydrogen in second endless tube
For 100-2000 × 10-6, it is remaining for propylene.Gas phase kettle pressure is 0.1-2.0MPa, and gas phase kettle temperature degree is 70-80 DEG C, gas phase kettle
Middle ethylene and ethylene and the mol ratio (C=of propylene sum2/ C=2+ C=3(mol/mol) it is) 0.01-0.5, hydrogen and second in gas phase kettle
Volume ratio (the H of alkene and propylene sum2/ C=2+ C=3(v/v) it is) 0.01-0.1.
High-impact transparent polypropylene resin of the present invention, including the raw material of following parts by weight：
Random impact polypropylene resin, clarifier 2000-4000ppm, antioxidant 1000-3000ppm, lubricant 200-800ppm,
Acid-acceptor 500-1000ppm.
Wherein：
Clarifier is phosphoric acid salt or glucitols clarifier, but is not limited to this, and its consumption is 2000-4000ppm, that is,
Say that clarifier accounts for the 2000-4000ppm of all raw material total amounts, preferred 2800-3500ppm.
Antioxidant is one or two in Hinered phenols antioxidant or phosphite antioxidant, commercially available prod, consumption
1000-3000ppm, preferred 2000ppm.Antioxidant is preferably antioxidant 1010 and 168 complex, both compounding weight ratios
For 1:1.
Acid-acceptor is stearate, such as calcium stearate, zinc stearate or sodium stearate, the preferred calcium stearate of acid-acceptor, is abbreviated as
Cast。
Lubricant is glyceryl monostearate, fatty acid metal salts, fatty acid amide or wax；It is preferred that glyceryl monostearate, its change
Scientific name is single 18 (alkane) acid glycerine ester, abbreviation monoglyceride GMS.
High-impact transparent polypropylene resin of the present invention, can be used for injector for medical purpose, household clear plastic articles, household electrical appliances portion
Part etc., meets medical apparatus health, packaging for foodstuff health demand, and is capable of achieving the double effectses of high transparency high-impact.
All raw materials are carried out melting mixing pelletize and are prepared i.e. by the preparation method of high-impact transparent polypropylene resin of the present invention
Can.
In sum, the present invention has advantages below：
(1) present invention includes the random impact polypropylene resin that a kind of propylene monomer and vinyl monomer polymerization are obtained, wherein ethylene list
In 4.0-8.0%, 1-3% therein take part in random copolymerization reaction and define atactic copolymerized polypropene, 3-5% ginsengs the weight content of body
Impact copolymer polypropylene is defined with crushing-resistant copolymerization reaction.Atactic copolymerized polypropene part to improve final products the transparency and
The compatibility for increasing homopolymerization part with anti-impact part has positive role, and impact copolymer polypropylene part is risen to the impact resilience for improving product
To decisive role, compared with common impact polypropylene, in the resin, crushing-resistant copolymerization moiety content is few, good dispersion, Neng Gouyou
Effect absorbs impact energy blocks the crackle of initiation, to greatly improving while impact resilience, not resulting in adverse effect to the transparency.
Due to above construction featuress, the characteristics of make resin of the present invention be provided simultaneously with high-impact and high transparency.
(2) the invention provides a kind of random impact polypropylene resin, generates COPP with ethylene copolymerization by propylene,
Including random copolymerization and crushing-resistant copolymerization two kinds of polymer, resin impact resilience, the transparency is made to reach higher balance.The resin
Can be used for injector for medical purpose, household clear plastic articles, appliances parts etc., solve the problems, such as the easy fragmentation of opaque products.With
The method for adding elastic body toughening in random polypropylene is compared, and the acrylic resin transparency obtained by the invention is high, impact resilience 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, household electrical appliances
Part etc., meets medical apparatus health, packaging for foodstuff health demand, and is capable of achieving the double effectses of high transparency high-impact, with
The commercial routes for adding elastic body toughening in random transparent polypropylene are compared, the resin of the present invention have transparent anti-impact good combination property,
Application cost is low, rigidity is high, viscosity is low for processing, easy-formation the features such as.
(4) present invention achieves high balance of the acrylic resin in terms of impact resilience and the transparency.
Description of the drawings
Fig. 1 is random impact polypropylene resin, atactic copolymerized polypropene resin and impact copolymer polypropylene resin three prepared by the present invention
The spectrogram of person.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Converging operationJu Hecaozuo employed in the present invention is on 70,000 tons of annual bicyclic pipes, the Sphripol polyplants of single gas phase kettle
Carry out, but be capable of achieving the device not limited to this of the present invention.Ziegler natta catalyst and electron donor are adopted in embodiment,
Combined polymerization is carried out to gas phase kettle and ethylene after bicyclic pipe Liquid-phase reactor is passed through propylene and hydrogen is polymerized, the polymer for obtaining
By double screw extruder pelletize after mixing with additive metering, final high-impact high transparency acrylic resin copolymer product is obtained.
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 the component of raw material used in 1 and
One hurdle of mass fraction；The polymerization technique and technological parameter of the random impact polypropylene resin in raw material random anti-impact poly- third in being shown in Table 1
One hurdle of polymerization technique and technological parameter of olefine resin；The ethylene contents of the random part of random impact polypropylene resin, anti-impact part
Ethylene contents and MFR be shown in Table one hurdle of parameter of random impact polypropylene resin in 1, the high-impact transparent polypropylene for preparing
The performance of resin is shown in Table one hurdle of performance of product in 1.
Raw material level performance characterization of corresponding comparative example 1-4 etc. is shown in Table 2.
Performance test institute's accepted standard is carried out to naval stores in embodiment 1-4 and comparative example 1-4 and method is as follows：
Melt mass flow rate：Carry out by GB/T 3682-2000；
Simply supported beam notch impact strength：Test by GB/T 1043.1-2008, wherein low-temperature process is -20 DEG C of placements 2 hours,
Room temperature processing procedure is 23 DEG C and places 24 hours；
Mist degree：Carry out according to GB/T 2410-2008, when not marking, sample thickness is 1mm；
The modulus of elasticity in static bending, 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
The random impact polypropylene resin and other different types of acrylic resins prepared to the present invention using infrared spectrometer is carried out
Infrared spectrum sign.It is resin of the present invention, atactic copolymerized polypropene resin, impact copolymer polypropylene tree from top to bottom successively
The spectrogram of three kinds of products of fat.Resin wherein of the invention is in 731cm-1、720cm-1There are obvious absorption peaks position, shows wherein
There is long ethylene segment i.e. impact copolymer again in the polymerization that there is random pattern.On middle atactic copolymerized polypropene spectrogram only
In 731cm-1There is obvious absworption peak position, shows in the product ethylene, propylene monomer mainly based on random copolymerization, most under
In 720cm on the crushing-resistant copolymerization product spectrogram in face-1、730cm-1There is long ethylene segment in then showing product in the absorption of position,
Mainly impact copolymer.
Claims (10)
1. a kind of high-impact transparent polypropylene resin, it is characterised in that：Including random impact polypropylene resin, the random anti-impact is gathered
Allyl resin is that propylene monomer and vinyl monomer polymerization are obtained, and wherein the weight content of vinyl monomer is in 4.0-8.0%, 1-3% ginsengs
Atactic copolymerized polypropene is defined with random copolymerization reaction, 3-5% take part in crushing-resistant copolymerization reaction and define crushing-resistant copolymerization poly- third
Alkene.
2. high-impact transparent polypropylene resin according to claim 1, it is characterised in that：The weight content of vinyl monomer exists
4.0-6.0%.
3. high-impact transparent polypropylene resin according to claim 1, it is characterised in that：Randomly impact polypropylene resin is
Propylene monomer and vinyl monomer are polymerized what is obtained in the presence of ziegler natta catalyst.
4. high-impact transparent polypropylene resin according to claim 1, it is characterised in that：Random impact polypropylene resin
MFR is 1-30g/10min.
5. high-impact transparent polypropylene resin according to claim 1, it is characterised in that：The random of 1mm thickness thin slices resists
Rush acrylic resin mist degree≤13%, simply supported beam notch impact strength >=13kJ/m2。
6. according to the arbitrary described high-impact transparent polypropylene resin of claim 1-5, it is characterised in that：Including following weight portion
Several raw materials：
Random impact polypropylene resin, clarifier 2000-4000ppm, antioxidant 1000-3000ppm, lubricant 200-800ppm,
Acid-acceptor 500-1000ppm.
7. high-impact transparent polypropylene resin according to claim 6, it is characterised in that：Clarifier is phosphoric acid salt or mountain
Pears alcohols clarifier.
8. high-impact transparent polypropylene resin according to claim 6, it is characterised in that：Antioxidant is Hinered phenols antioxygen
One or two in agent or phosphite antioxidant.
9. high-impact transparent polypropylene resin according to claim 6, it is characterised in that：Acid-acceptor is stearate.
10. high-impact transparent polypropylene resin according to claim 6, it is characterised in that：Lubricant is that monostearate is sweet
Grease, fatty acid metal salts, fatty acid amide or wax.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245194A (en) * | 2017-04-14 | 2017-10-13 | 中国石油化工股份有限公司 | A kind of preparation method of high strength heat resistant atactic copolymerized polypropene resin |
| 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 |
| CN109627596A (en) * | 2017-10-09 | 2019-04-16 | 中国石油化工股份有限公司 | With polypropylene masterbatch, preparation method and the application for increasing mist degree effect |
| CN110256619A (en) * | 2019-06-24 | 2019-09-20 | 中国石油化工股份有限公司 | A kind of polyacrylic polymer, preparation method and its high-gloss polypropylene resin of preparation |
| 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 |
| CN114058113A (en) * | 2020-08-10 | 2022-02-18 | 中国石油天然气股份有限公司 | High-impact transparent polypropylene resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245194A (en) * | 2017-04-14 | 2017-10-13 | 中国石油化工股份有限公司 | A kind of preparation method of high strength heat resistant atactic copolymerized polypropene resin |
| 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 |
| CN109627596A (en) * | 2017-10-09 | 2019-04-16 | 中国石油化工股份有限公司 | With polypropylene masterbatch, preparation method and the application for increasing mist degree effect |
| 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 |
| CN110256619A (en) * | 2019-06-24 | 2019-09-20 | 中国石油化工股份有限公司 | A kind of polyacrylic polymer, preparation method and its high-gloss polypropylene resin of preparation |
| 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 |
| CN114058113A (en) * | 2020-08-10 | 2022-02-18 | 中国石油天然气股份有限公司 | High-impact transparent polypropylene resin and preparation method thereof |
| 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 |
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