CN111100380A - Polypropylene resin for hot-filling bottle - Google Patents
Polypropylene resin for hot-filling bottle Download PDFInfo
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- CN111100380A CN111100380A CN201811246954.5A CN201811246954A CN111100380A CN 111100380 A CN111100380 A CN 111100380A CN 201811246954 A CN201811246954 A CN 201811246954A CN 111100380 A CN111100380 A CN 111100380A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
Abstract
The invention provides a polypropylene resin for hot-filling bottles, which comprises a polypropylene resin base material, an antioxidant, a nucleating agent and an acid neutralizer; wherein: the polypropylene resin base material is propylene/1-butylene random copolymerization polypropylene, the content of butylene is 1-10 wt%, the melting temperature is 140-165 ℃, and the melt flow rate is 3.0-25.0 g/10 min. Compared with the existing ethylene/propylene random copolymerization polypropylene, the propylene/1-butylene random copolymerization polypropylene resin has better crystallization capacity, higher heat resistance and rigidity, the heat distortion temperature of 80-90 ℃ and the flexural modulus of 1200-1400 MPa, is suitable for injection stretch blow molding and can be applied to hot-filling beverage bottles.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a polypropylene resin, and particularly relates to a polypropylene resin for a hot-filling bottle.
Background
After years of rapid development of the Chinese beverage industry, bottled beverages grow at an average annual high growth rate of two digits, and currently, Polyester (PET) bottle packages occupy a major share of the domestic beverage packaging market. The polypropylene (PP) bottle has excellent appearance in hot-filling packaging aspects such as tea, fruit and vegetable juice, sports drinks, health-care drinks and the like due to the characteristic of high temperature resistance, and gradually replaces a PET bottle; in addition, it is excellent in safety, environmental protection, hygiene and taste retention of contents, and is gradually introduced into the field of dairy products instead of PE bottles.
The hot filling is generally carried out at 80-90 deg.C, and water spray sterilization is carried out at 90 deg.C for about 15 min. The PP bottle can bear hot filling temperature as high as 96 ℃, while the PET bottle can bear hot filling temperature of 54-65 ℃ when not subjected to heat setting, so that the PET bottle needs to be subjected to heat setting treatment, but even if the PET bottle has the hot filling temperature of only about 85 ℃, so that the PP bottle has more advantages in the field of hot filling.
At the above hot-fill and sterilization temperatures, the PP bottles are required to maintain sufficient rigidity and heat resistance without deformation, which requires a PP raw material having a high flexural modulus and a high heat distortion temperature. The filled beverage can be refrigerated at low temperature or transported, stored and used at low ambient temperature, and the PP bottle is resistant to impact and cracking, so that the PP raw material has good toughness. Homopolypropylene has good rigidity and heat resistance, but poor toughness and transparency, and thus, ethylene/propylene random copolymerization is generally used to improve the toughness and transparency of PP, but its rigidity and heat resistance are significantly deteriorated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the polypropylene resin for the hot filling bottle, which has better rigidity and heat resistance, better toughness and transparency and meets the requirements of the hot filling bottle produced by an injection stretch blow molding process.
The following is a specific technical solution of the present invention.
A polypropylene resin for hot-fill bottles, comprising: polypropylene resin base stock, antioxidant, nucleating agent and acid neutralizer; the polypropylene resin is prepared by melting, mixing and granulating a polypropylene resin base material, an antioxidant, a nucleating agent and an acid neutralizer; the mass ratio of the polypropylene resin base material to the antioxidant to the nucleating agent to the acid neutralizer is 100: (0.02-0.25): (0.01-0.10): (0.01 to 0.08);
the polypropylene resin base material is propylene/1-butylene random copolymerization polypropylene, the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant, the nucleating agent is organic phosphate nucleating agent, and the acid neutralizer is calcium stearate or hydrogenated talcum powder.
Further, the propylene/1-butene random copolymerization polypropylene has the butene content of 1-10 wt%, the melting temperature of 140-165 ℃ and the melt flow rate of 3.0-25.0 g/10 min.
Further, the butene content of the propylene/1-butene random copolymerization polypropylene is 3-8 wt%.
Further, the melt flow rate of the propylene/1-butene random copolymerization polypropylene is 5.0-15.0 g/10 min.
Further, the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.3-1: 8.
Further, the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.8-1: 6.
Further, the hindered phenol antioxidant is 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4 hydroxybenzyl) benzene or 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Further, the organic phosphate nucleating agent is one or two of bis [2,2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate ] aluminum hydroxide or 2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) sodium phosphate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the resin base material adopted by the invention is propylene/1-butylene random copolymerization polypropylene, which replaces the existing ethylene/propylene random copolymerization polypropylene, and the two have similar toughness and transparency, but the propylene/butylene random copolymerization polypropylene has better crystallization capability and higher heat resistance and rigidity, the heat deformation temperature reaches 80-90 ℃, the flexural modulus reaches 1200-1400 MPa, and compared with the ethylene-propylene random copolymerization polypropylene, the heat deformation temperature is 70-80 ℃, and the flexural modulus is 900-1100 MPa.
(2) The melt flow rate of the resin base material is preferably 5.0-15.0 g/10min, and the resin base material is suitable for injection, stretching and blow molding and can be applied to hot-filling beverage bottles. The resin base material has good crystallization capacity, and can be rapidly crystallized at a higher temperature by matching with a nucleating agent, so that the molding speed is increased, and the production efficiency is improved by 25-35%.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Examples 1 to 3
The characteristics of the propylene/1-butene random copolymer polypropylene resin used in the examples are shown in Table 1, and the melt flow rate is 8-12 g/10 min.
The antioxidant in this example is a mixture of 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and tris (2, 4-di-tert-butylphenyl) phosphite in a ratio of 1: 1; the nucleating agent adopts 2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) sodium phosphate; the acid neutralizer is calcium stearate. The ratio of the polypropylene resin base material to the antioxidant, the nucleating agent and the acid neutralizer is 100:0.15:0.06: 0.05.
In the embodiment, the propylene/1-butene random copolymerization polypropylene resin base material is mixed with auxiliary agents such as an antioxidant, a nucleating agent, an acid neutralizer and the like, and the propylene/1-butene random copolymerization polypropylene resin is prepared by melt extrusion granulation.
The propylene/1-butene random copolymer polypropylene resins used in examples 4 to 7 below all had butene contents of 7.4 Wt.%, which are the same as in example 1.
Example 4
The flow rate of the adopted propylene/1-butene random copolymerization polypropylene resin melt is 3.0g/10min, the antioxidant adopts a mixture of 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4 hydroxybenzyl) benzene and tri (2, 4-di-tert-butylphenyl) phosphite ester, and the ratio of the two is 1: 0.3; the nucleating agent adopts 2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) sodium phosphate; the acid neutralizer is calcium stearate. The ratio of the polypropylene resin base material to the antioxidant, the nucleating agent and the acid neutralizer is 100:0.02:0.01: 0.01. The procedure for preparing a propylene/1-butene random copolymer polypropylene resin was the same as in example 1.
Example 5
The melt flow rate of the adopted propylene/1-butene random copolymerization polypropylene resin is 25.0g/10min, the antioxidant adopts a mixture of 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and tri (2, 4-di-tert-butylphenyl) phosphite ester, and the ratio of the two is 1: 8; the nucleating agent adopts 2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) sodium phosphate; the acid neutralizer is hydrogenated talcum powder. The ratio of the polypropylene resin base material to the antioxidant, the nucleating agent and the acid neutralizer is 100:0.25:0.10: 0.08. The procedure for preparing a propylene/1-butene random copolymer polypropylene resin was the same as in example 1.
Example 6
The flow rate of the adopted propylene/1-butylene random copolymerization polypropylene resin melt is 5.0g/10min, the antioxidant adopts the mixture of tetra 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4 hydroxybenzyl) benzene and diphosphorous acid bis (2, 4-di-tert-butylphenyl) pentaerythritol ester, and the ratio of the two is 1: 0.8; the nucleating agent adopts bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) phosphate ] aluminum hydroxide; the acid neutralizer is calcium stearate. The ratio of the polypropylene resin base material to the antioxidant, the nucleating agent and the acid neutralizer is 100:0.10:0.05: 0.03. The procedure for preparing a propylene/1-butene random copolymer polypropylene resin was the same as in example 1.
Example 7
The flow rate of the adopted propylene/1-butylene random copolymerization polypropylene resin melt is 15.0g/10min, the antioxidant adopts a mixture of 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and diphosphorous acid bis (2, 4-di-tert-butylphenyl) pentaerythritol ester, and the ratio of the two is 1: 6; the nucleating agent adopts bis [2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) phosphate ] aluminum hydroxide; the acid neutralizer is hydrogenated talcum powder. The ratio of the polypropylene resin base material to the antioxidant, the nucleating agent and the acid neutralizer is 100:0.20:0.08: 0.05. The procedure for preparing a propylene/1-butene random copolymer polypropylene resin was the same as in example 1.
Comparative examples 1 to 3
The characteristics of the ethylene/propylene random copolymer polypropylene of comparative examples 1 to 2 and the homo-polypropylene resin of comparative example 3 are shown in Table 1, and the melt flow rate is 8 to 12g/10 min.
In the comparative example, the ethylene/propylene random copolymerization polypropylene resin base stock and the homopolymerization polypropylene resin base stock are respectively mixed with the antioxidant, the nucleating agent, the acid neutralizer and other auxiliary agents, and the comparative example polypropylene resin is prepared by melt extrusion granulation; the varieties and the addition amounts of the antioxidant, the nucleating agent and the acid neutralizer are the same as those of the examples 1 to 3.
The physical and mechanical properties of the polypropylene resins of the examples and comparative examples are compared in tables 2 and 3.
The tensile yield stress is tested according to GB/T1040.2;
flexural modulus was tested according to GB/T9341;
the impact strength of the notch of the simply supported beam is tested according to GB/T1043.1;
the heat distortion temperature is tested according to GB/T1634.2;
the haze is tested according to GB/T2410;
ethylene and butene contents were determined by infrared spectroscopy: wave number of 720-730 cm-1The characteristic peak of ethylene is obtained to obtain the ethylene content of 767cm-1Obtaining the content of the butylene by using the butylene characteristic peak;
melting point, crystallization temperature and crystallinity were measured by Differential Scanning Calorimeter (DSC): under the protection of nitrogen, taking a small amount of polypropylene sample, heating to 200 ℃ at the speed of 10 ℃/min, keeping the temperature for 5min, then cooling to room temperature at the speed of 10 ℃/min, recording a melting and crystallization curve, and obtaining a melting point, a crystallization temperature and a crystallinity.
TABLE 1 characteristics of polypropylene resins of examples and comparative examples
TABLE 2 physical and mechanical properties of polypropylene resins of examples and comparative examples
As seen from Table 2, although the homopolypropylene has higher modulus and heat distortion temperature, the homopolypropylene has poorer impact strength and higher haze, the addition of α -olefin copolymerization can improve the impact strength and haze of the polypropylene, but the modulus and heat distortion temperature of the ethylene-propylene copolymerization polypropylene are rapidly reduced along with the increase of the ethylene content, which is not beneficial to hot filling.
By combining tables 1 and 2, when the melting points of the ethylene-propylene copolymer polypropylene and the propylene-butylene copolymer polypropylene reach 148 ℃, the ethylene mass percentage content of the ethylene-propylene random copolymer polypropylene is 2.9%, the butylene mass percentage content of the propylene-butylene random copolymer polypropylene is increased to 7.4%, the crystallinity of the propylene-butylene random copolymer polypropylene is 43.1%, the heat distortion temperature is 88 ℃, and the flexural modulus is 1320MPa, which are respectively increased by 11.9%, 12.8% and 25.7% compared with the ethylene-propylene random copolymer polypropylene, and the impact strength and the haze of the ethylene-propylene random copolymer polypropylene and the propylene-butylene copolymer polypropylene are basically the. Therefore, the polypropylene random copolymer of the invention is more suitable for the application of hot filling bottles.
TABLE 3 physical and mechanical Properties of examples 1 and 4 to 7
As shown in Table 3, the polypropylene random copolymer of propane and butane of the present invention has better rigidity, toughness, heat resistance and transparency under different melt flow rates and formulations.
Claims (8)
1. The polypropylene resin for the hot filling bottle is characterized by comprising the following components in percentage by weight: polypropylene resin base stock, antioxidant, nucleating agent and acid neutralizer; the polypropylene resin is prepared by melting, mixing and granulating a polypropylene resin base material, an antioxidant, a nucleating agent and an acid neutralizer; the mass ratio of the polypropylene resin base material to the antioxidant to the nucleating agent to the acid neutralizer is 100: (0.02-0.25): (0.01-0.10): (0.01 to 0.08);
the polypropylene resin base material is propylene/1-butylene random copolymerization polypropylene, the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant, the nucleating agent is organic phosphate nucleating agent, and the acid neutralizer is calcium stearate or hydrogenated talcum powder.
2. The polypropylene resin for hot-fill bottles of claim 1, wherein the propylene/1-butene random copolymer polypropylene has a butene content of 1 to 10 wt%, a melting temperature of 140 to 165 ℃, and a melt flow rate of 3.0 to 25.0g/10 min.
3. The polypropylene resin for hot-fill bottles of claim 2, wherein the propylene/1-butene random copolymer polypropylene has a butene content of 3 to 8 wt%.
4. The polypropylene resin for hot-fill bottles of claim 2, wherein the propylene/1-butene random copolymer polypropylene has a melt flow rate of 5.0 to 15.0g/10 min.
5. The polypropylene resin for hot-fill bottles as claimed in claim 1, wherein the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.3-1: 8.
6. The polypropylene resin for hot-fill bottles as claimed in claim 5, wherein the weight ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1: 0.8-1: 6.
7. The polypropylene resin for hot-fill bottles of claim 5, wherein said hindered phenolic antioxidant is 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite or bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
8. The polypropylene resin for hot-fill bottles of claim 1, wherein the nucleating agent of the organic phosphate salt is one or both of bis [2,2 '-methylene-bis (4, 6-di-tert-butylphenyl) phosphate ] aluminum hydroxide and sodium 2, 2' -methylene-bis (4, 6-di-tert-butylphenyl) phosphate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811246954.5A CN111100380A (en) | 2018-10-25 | 2018-10-25 | Polypropylene resin for hot-filling bottle |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811246954.5A CN111100380A (en) | 2018-10-25 | 2018-10-25 | Polypropylene resin for hot-filling bottle |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276622A (en) * | 2020-09-27 | 2022-04-05 | 合肥杰事杰新材料股份有限公司 | Heat-resistant transparent polypropylene composition and preparation method and application thereof |
| CN114426735A (en) * | 2020-09-30 | 2022-05-03 | 中国石油化工股份有限公司 | Polypropylene resin for bottle caps and preparation method thereof |
| CN114801391A (en) * | 2021-01-20 | 2022-07-29 | 内蒙古蒙牛乳业（集团）股份有限公司 | Composite sheet and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724200A (en) * | 2008-10-31 | 2010-06-09 | 中国石化上海石油化工股份有限公司 | Polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding |
| CN102234400A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | High transparent polypropylene composition and preparation method thereof |
| CN102453282A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
-
2018
- 2018-10-25 CN CN201811246954.5A patent/CN111100380A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724200A (en) * | 2008-10-31 | 2010-06-09 | 中国石化上海石油化工股份有限公司 | Polypropylene resin used for manufacturing medical infusion bottle by injection stretch blow moulding |
| CN102234400A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | High transparent polypropylene composition and preparation method thereof |
| CN102453282A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 贾红兵等: "聚合物改性原理", vol. 1, 中国轻工业出版社, pages: 183 - 184 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276622A (en) * | 2020-09-27 | 2022-04-05 | 合肥杰事杰新材料股份有限公司 | Heat-resistant transparent polypropylene composition and preparation method and application thereof |
| CN114276622B (en) * | 2020-09-27 | 2023-10-20 | 合肥杰事杰新材料股份有限公司 | Heat-resistant transparent polypropylene composition and preparation method and application thereof |
| CN114426735A (en) * | 2020-09-30 | 2022-05-03 | 中国石油化工股份有限公司 | Polypropylene resin for bottle caps and preparation method thereof |
| CN114801391A (en) * | 2021-01-20 | 2022-07-29 | 内蒙古蒙牛乳业（集团）股份有限公司 | Composite sheet and preparation method thereof |
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