# US 12,767,803 B2 · Polypropylene composition, preparation method therefor, and article made therefrom

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- Number: US 12,767,803 B2
- Document ID: US12767803B2
- Status: Granted
- Kind: B2
- Application number: 18/042,481
- Filed: 2021-08-20
- Published: 2023-10-12
- Granted: 2026-10-20
- Earliest claimed: 2020-08-27
- Assignees: China Petroleum & Chemical Corporation; Beijing Research Institute of Chemical Industry
- Applicants: China Petroleum & Chemical Corporation; Beijing Research Institute of Chemical Industry, China Petroleum & Chemical Corporation
- Inventors: Xiaomeng Zhang; Wenbo Song; Fasheng Zou; Huijie Hu; Dezhan Li; Lusheng Wang; Mengyao Zhao; Qi Zhang; Zhenjie Liu; Hao Yuan
- Web page: https://patentgrep.com/patent/US12767803B2

## CPC

- C08L 23/12: Polypropene
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A polypropylene composition, a preparation method therefor, and an article made therefrom, the polypropylene composition comprising: (a) 70-95% by weight of a crystalline homo-polypropylene having a isotactic pentad fraction of 96% or more and forming a continuous matrix phase in the polypropylene composition; (b) 5-30% by weight of an ethylene-propylene elastic copolymer containing 20-35% by weight of an ethylene structure unit and 65-80% by weight of a propylene structure unit, and forming a dispersed rubber phase in the continuous matrix phase, such that the rubber phase can at least partially deform under an orientation force and form an orientation state structure, wherein the ratio of melt mass flow rate measured at 230° C. and a 2.16 kg load of the crystalline homo-polypropylene and the polypropylene composition is 0.5-2.0. The polypropylene composition and article have a high gloss and good mechanical properties, and the preparation method is simple, low in cost and environmentally friendly; and the article can be used in electric appliances, homes, packaging, automobiles, toys, or the medical field.

## Claims

### Claim 1

A polypropylene composition comprising:
(a) 70-95% by weight of a crystalline homopolypropylene as component A, with an isotactic pentad fraction of 96% or more; wherein the crystalline homopolypropylene forms a continuous matrix phase in the polypropylene composition; and
(b) 5-30% by weight of an ethylene-propylene elastic copolymer as component B, wherein based on the total weight of the ethylene-propylene elastic copolymer, the ethylene-propylene elastic copolymer contains 20-35% by weight of ethylene structural units of ethylene structural units, and 65-80% by weight of propylene structural units, of propylene structural units; the ethylene-propylene elastic copolymer forms a dispersed rubber phase in the continuous matrix phase, the rubber phase is capable of being deformed at least partially under the action of orientation force and forming an oriented structure;
wherein the ratio of the melt mass flow rate of the crystalline homopolypropylene to that of the polypropylene composition measured at 230° C. under a load of 2.16 kg according to GB/T 3682.1-2018 ranges from 0.5 to 2.0.

### Claim 2 (depends on 1)

The polypropylene composition according to claim 1, wherein when no orientation force acts, the rubber phase is spherical or nearly spherical particles, and the rubber phase particles have an average size ranging from 0.03 μm to 3.0 μm, as determined by SEM method.

### Claim 3 (depends on 1)

The polypropylene composition according to claim 1, wherein after the orientation force acts, at least 50% of the rubber phase particles have an aspect ratio greater than 2, based on the total number of rubber phase particles in the SEM photograph.

### Claim 4 (depends on 1)

The polypropylene composition according to claim 1, wherein the orientation force refers to an external field force that is capable of causing an object to be oriented, the orientation refers to the parallel alignment of the object along the direction of the external field force; the oriented structure is a structure in which the longitudinal axes formed by deformation and elongation of the rubber phase particles under the action of the orientation force are aligned parallel to each other along a direction.

### Claim 5 (depends on 1)

The polypropylene composition according to claim 1, wherein the crystalline homopolypropylene has a melt mass flow rate ranging from 5 g/10 min to 200 g/10 min at 230° C. under a load of 2.16 kg according to GB/T 3682.1-2018; and/or the polypropylene composition has a melt mass flow rate ranging from 5 g/10 min to 100 g/10 min at 230° C. under a load of 2.16 kg according to GB/T 3682.1-2018.

### Claim 6 (depends on 1)

The polypropylene composition according to claim 1, wherein the intrinsic viscosity of the polypropylene composition ranges from 1.0 dL/g to 2.5 dL/g; and/or the intrinsic viscosity of xylene solubles in the polypropylene composition ranges from 1.0 dL/g to 4.0 dL/g; and/or the ratio of the intrinsic viscosity of xylene solubles to the intrinsic viscosity of the crystalline homopolypropylene in the polypropylene composition ranges from 0.7 to 2.6.

### Claim 7 (depends on 1)

The polypropylene composition according to claim 1, wherein the molecular weight distribution Mw/Mn of the polypropylene composition is less than or equal to 5, as determined by gel permeation chromatography (GPC) analysis relative to polystyrene standards.

### Claim 8 (depends on 1)

The polypropylene composition according to claim 1, wherein the polypropylene composition has a 60° angle gloss of greater than or equal to 80%.

### Claim 9 (depends on 8)

The polypropylene composition according to claim 8, wherein the polypropylene composition further has one or more of the following properties:
1) Parallel shrinkage ratio of less than or equal to 1.15;
2) Vertical shrinkage ratio of less than or equal to 1.36;
3) Flexural modulus of greater than or equal to 1000 MPa;
4) Charpy notched impact strength at room temperature of greater than or equal to 5 kJ/m2; and
5) Heat deformation temperature of greater than or equal to 90° C.

### Claim 10 (depends on 1)

The polypropylene composition according to claim 1, wherein the polypropylene composition further comprises: (c) a nucleating agent as component C, which is at least one selected from the group consisting of carboxylic acids and their metal salts, sorbitol, aryl phosphates, dehydroabietic acid and its salts, aromatic amides, aromatic amines, rare earth compounds, condensed ring compounds having a quasi-planar structure, and polymeric nucleating agents.

### Claim 11 (depends on 1)

The polypropylene composition according to claim 1, wherein the polypropylene composition further comprises other auxiliary, said other auxiliary is at least one selected from the group consisting of antioxidants, antistatic agents and colorants.

### Claim 12 (depends on 1)

The polypropylene composition according to claim 1, wherein the polypropylene composition is in the form of powders or pellets.

### Claim 13 (depends on 1)

A method for the preparation of the polypropylene composition according to claim 1, comprising:
(1) under first olefin polymerization conditions, contacting and reacting propylene monomers with a stereoselective Ziegler-Natta catalyst, and removing the unreacted monomers from the mixture obtained after the contacting and reacting to obtain a product “a”, said product “a” comprising component A; and
(2) under second olefin polymerization conditions, contacting and reacting ethylene monomers and propylene monomers with the product “a” obtained in step (1) under gas phase, and removing the unreacted monomers from the mixture obtained after the contacting and reacting to obtain product “b” comprising component A and component B, wherein the product “b” is the polypropylene composition.

### Claim 14 (depends on 13)

The method according to claim 13, wherein the stereoselective Ziegler-Natta catalyst comprises:
(i) a solid catalyst component, containing a product obtainable from a reaction of a magnesium source, a titanium source and an internal electron donor; wherein the internal electron donor is selected from the group consisting of monocarboxylic acid esters, dicarboxylic acid esters, phosphoric acid ester compounds, diether compounds and combinations thereof; the magnesium source is one or more selected from magnesium halide, magnesium alcoholate, magnesium halogenated alcoholate and magnesium halide adduct carrier; the titanium source is one or more selected from the titanium compounds represented by the general formula Ti(OR)4-mXm, wherein m is an integer of 0-4, R is a C1-C20 alkyl, X is halogen;
(ii) an organoaluminum compound; and
(iii) optionally an external electron donor, which is an organosilicon compound having the general formula RnSi(OR′)4-n, where 0<n≤3, R is selected from hydrogen atom, halogen, alkyl, cycloalkyl, aryl and haloalkyl, and R′ is selected from alkyl, cycloalkyl, aryl and haloalkyl.

### Claim 15 (depends on 14)

The method according to claim 14, wherein the internal electron donor is at least one selected from the group consisting of benzoate, malonate, phthalate and succinate.

### Claim 16 (depends on 14)

The method according to claim 14, wherein the internal electron donor is an internal electron donor compounded by a phosphoric acid ester compound and a diether compound.

### Claim 17 (depends on 14)

The method according to claim 14, wherein the molar ratio of the magnesium source in terms of magnesium element, the titanium source in terms of titanium element and the internal electron donor is 1:(20-150):(0.1-0.9); and/or the amount ratio of the solid catalyst component to the organoaluminum compound in terms of titanium/aluminum molar ratio is 1:(25-100); and/or the weight ratio of the organoaluminum compound to the external electron donor is (0-150):1.

### Claim 18 (depends on 13)

The method according to claim 13, wherein in step (1), the first olefin polymerization conditions are liquid phase polymerization conditions or gas phase polymerization conditions; the liquid phase polymerization conditions comprise: using hydrogen as a molecular weight regulator, a polymerization temperature ranging from 0° C. to 150° C.; and a polymerization pressure higher than the saturated vapor pressure of propylene at the corresponding polymerization temperature; the gas phase polymerization conditions comprise: using hydrogen as a molecular weight regulator, a polymerization temperature of ranging from 0° C. to 150° C.; and a polymerization pressure greater than or equal to normal pressure; the hydrogen/propylene molar ratio used in step (1) ranges from 0.0010 to 0.0060.

### Claim 19 (depends on 13)

The method according to claim 13, wherein in the reaction system of step (2), the molar ratio of ethylene/(ethylene+propylene) ranges from 0.1 to 0.4; and/or the temperature of olefin gas phase polymerization ranges from 40° C. to 100° C.; and the pressure ranging from 0.6 MPa to 1.4 MPa; and/or the hydrogen/ethylene molar ratio ranges from 0.02 to 0.70.

### Claim 20 (depends on 13)

The method according to claim 13, wherein the method further comprises step (3): subjecting the product “b” obtained in step (2) and a nucleating agent and optionally other auxiliaries to mixing.

### Claim 21 (depends on 1)

An article prepared from the polypropylene composition according to claim 1, wherein at least a part of the rubber phase of the rubber phase particles is deformed and forms an oriented structure.

### Claim 22 (depends on 21)

The article according to claim 21, wherein the article is a product or a part of the product, wherein the product is selected from housings for home appliances, automotive interior parts, children's toys, home storage products and medical disposable syringes.

### Claim 23 (depends on 1)

The polypropylene composition according to claim 1, wherein the crystalline homopolypropylene has an isotactic pentad fraction of 97% or more.

### Claim 24 (depends on 1)

The polypropylene composition according to claim 1, wherein the ethylene-propylene elastic copolymer contains 25-35% by weight of ethylene structural units, and 65-75% by weight of propylene structural units.

### Claim 25 (depends on 1)

The polypropylene composition according to claim 1, wherein the ratio of the melt mass flow rate of the crystalline homopolypropylene to that of the polypropylene composition measured at 230° C. under a load of 2.16 kg according to GB/T 3682.1-2018 ranges from 0.9 to 1.5.

### Claim 26 (depends on 4)

The polypropylene composition according to claim 4, wherein the orientation force is tensile stress and/or shear stress which is applied to the polypropylene composition during the process of preparing an article using said composition.

### Claim 27 (depends on 4)

The polypropylene composition according to claim 4, wherein at least 80% of the rubber phase particles form an oriented structure, based on the total number of rubber phase particles in the SEM photograph.

### Claim 28 (depends on 5)

The polypropylene composition according to claim 5, wherein
the crystalline homopolypropylene has a melt mass flow rate ranging from 10 g/10 min to 100 g/10 min at 230° C. under a load of 2.16 kg according to GB/T 3682.1-2018; and/or
the polypropylene composition has a melt mass flow rate ranging from 6 g/10 min to 30 g/10 min at 230° C. under a load of 2.16 kg according to GB/T 3682.1-2018.

### Claim 29 (depends on 7)

The polypropylene composition according to claim 7, wherein the molecular weight distribution Mw/Mn of the polypropylene composition is less than or equal to 4.5, as determined by gel permeation chromatography (GPC) analysis relative to polystyrene standards.

### Claim 30 (depends on 8)

The polypropylene composition according to claim 8, wherein the polypropylene composition has a 60° angle gloss of greater than or equal to 90%.

### Claim 31 (depends on 8)

The polypropylene composition according to claim 8, wherein the polypropylene composition further has a haze of less than or equal to 50%.

### Claim 32 (depends on 9)

The polypropylene composition according to claim 9, wherein the polypropylene composition further has all of said properties.

### Claim 33 (depends on 14)

The method according to claim 14, wherein the magnesium source is spherical magnesium halide adduct.

### Claim 34 (depends on 14)

The method according to claim 14, wherein the organoaluminum compound is at least one selected from the group consisting of triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride, di-n-butylaluminum monochloride, diisobutylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride and n-hexylaluminum dichloride.

### Claim 35 (depends on 14)

The method according to claim 14, wherein the external electron donor is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane.

### Claim 36 (depends on 14)

The method according to claim 14, wherein the catalyst has been subjected to pre-complexation and/or pre-polymerization treatments.

### Claim 37 (depends on 16)

The method according to claim 16, wherein the molar ratio of the amount of the diether compound to that of the phosphoric acid ester compound is 1: (0.02-0.25).

### Claim 38 (depends on 16)

The method according to claim 16, wherein the phosphoric acid ester compound is at least one selected from the phosphoric acid ester compounds represented by formula (1),
wherein R1, R2 and R3 are each independently selected from C1-C4 linear or branched alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl or C7-C20 aralkyl; and
wherein the diether compound is at least one selected from the diether compounds represented by formula (2),
R1R2C(CH2OR3)(CH2OR4) formula (2)
wherein R1 and R2 are each independently selected from hydrogen, C1-C20 linear or branched alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl or C7-C20 alkaryl, R3 and R4 are each independently selected from C1-C10 alkyl.

### Claim 39 (depends on 38)

The method according to claim 38, wherein
the phosphoric acid ester compound is at least one selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxy phenyl phosphate, phenyl dimethyl phosphate, cresyl dibutyl phosphate, cumyl dimethyl phosphate, cumyl diethyl phosphate, cumyl dibutyl phosphate, phenyl xylyl phosphate, phenyl diisopropylphenyl phosphate, p-cresyl dibutyl phosphate, m-cresyl dibutyl phosphate, p-cumyl dimethyl phosphate, p-cumyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate and o-cresyl p-di-tert-butylphenyl phosphate; and
the diether compound is at least one selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane and 9,9-dimethoxymethylfluorene.

### Claim 40 (depends on 20)

The method according to claim 20, wherein in step (3) further pelletization is carried out.

### Claim 41 (depends on 21)

The article according to claim 21, wherein the article is an injection molded article.

### Claim 42 (depends on 21)

The article according to claim 21, wherein at least 80% of the rubber phase particles are deformed and form an oriented structure.

### Claim 43 (depends on 21)

The article according to claim 21, wherein both at a position within 10% of the thickness from the article surface and at a position of the core part beyond 10% of the thickness from the article surface, the rubber phase is deformed, elongated and forms an oriented structure.

### Claim 44 (depends on 21)

The article according to claim 21, wherein more than 50% of the rubber phase particles at a position within 10% of the thickness from the article surface have an aspect ratio greater than or equal to 4; and more than 50% of the rubber phase particles at a position of the core part beyond 10% of the thickness from the article surface have an aspect ratio greater than or equal to 2, based on the total number of the rubber phase particles at the corresponding position in the SEM photograph.