CN110669292A - Preparation method of toughened polypropylene resin - Google Patents

Preparation method of toughened polypropylene resin Download PDF

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CN110669292A
CN110669292A CN201911039762.1A CN201911039762A CN110669292A CN 110669292 A CN110669292 A CN 110669292A CN 201911039762 A CN201911039762 A CN 201911039762A CN 110669292 A CN110669292 A CN 110669292A
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polypropylene
resin
percent
toughened
catalyst
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曹建秋
马国玉
王辉
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China Petroleum and Chemical Corp
China Petrochemical Corp
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China Petrochemical Corp
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a preparation method of toughened polypropylene resin. Liquid propylene is used as a main raw material, an NDQ catalyst is adopted, ethylene with the mass percent of 0.8-1.4% of propylene is added, and random copolymerization polypropylene base resin with the molecular weight distribution Mw/Mn of 5.0-7.5 is produced on a Spheripol process single-ring pipe polypropylene device. Adding 5-15% of ultralow-density polyethylene resin in total mass fraction into the random copolymerization polypropylene base resin, adding an antioxidant and other auxiliary agent systems, fully mixing, extruding by a double-screw extruder, and granulating to obtain a toughened polypropylene product. The toughened polypropylene has good melting and sagging resistance and good toughness, particularly the notch impact strength of a simple beam at normal temperature can be obviously improved by more than 30 percent compared with the common polypropylene, and the toughened polypropylene is suitable for sheet extrusion and is used for processing and producing the packaging of trays, meal covers, food packaging containers, folding boxes, stationery, industrial parts and the like for plastic uptake molding.

Description

Preparation method of toughened polypropylene resin
Technical Field
The invention discloses a preparation method of toughened polypropylene resin. The polypropylene resin produced by the method has the characteristics of good melt-sagging resistance and good toughness, particularly the notch impact strength of the simple beam at normal temperature can be obviously improved by more than 30.0 percent compared with the common polypropylene, and the polypropylene resin is suitable for sheet extrusion and is used for processing and producing the packaging of trays, meal covers, food packaging containers, folding boxes, stationery, industrial parts and the like for plastic uptake molding.
Background
The polypropylene is one of the most promising thermoplastic polymer materials at present, compared with other general thermoplastic plastics, the polypropylene has the characteristics of small density, no toxicity, easy processing, good mechanical properties such as yield strength, surface strength and the like, outstanding stress cracking resistance, wear resistance, chemical stability, wide raw material source, low price and the like, and the application range of the polypropylene relates to the extremely wide fields of automobiles, household appliances, electronic appliance packaging, building materials, furniture and the like. However, polypropylene has poor impact resistance and is classified as one of brittle materials, which limits its application in some fields. As early as the 50 s in the 20 th century, the problem of toughening plastics has been studied to modify polypropylene. Polypropylene modification can be carried out by chemical and physical methods. The chemical method mainly adopts the methods of copolymerization, crosslinking, grafting and the like to change the molecular chain structure of the polypropylene so as to achieve the aim of modification. The physical modification is mainly to improve the insufficiency of the polypropylene performance by blending and compounding with other components.
At present, the main method for toughening and modifying polypropylene at home and abroad is physical modification, namely a mechanical blending method. Common modified materials include PE, BR, EPR, EPDM, POE, SEBS, nano materials and the like. In recent years, the reactive blending is reported to be carried out successively, and the reactive blending is that when PP and other polymers are blended, a reactive compatilizer is added as a third component, so that the toughening modification effect is more remarkable. Aoyeitui introduces the research of toughening polypropylene with different elastomers that PP is melted and blended with three different elastomers, namely POE, SEBS and OBC in a double screw extruder to prepare PP/elastomer blend, tests the mechanical property of the blend, compares the toughening efficiency of different elastomers and researches the brittle fracture surface appearance of the blend. The results show that: the 3 elastomers have toughening effect on PP, the SEBS has highest toughening efficiency on PP, the POE has the best comprehensive performance, and the OBC has good processability. But the mechanical blending often has the defects of uneven mixing, influence on the performance of PP and the like.
CN103665546B (application No. 201310608396.3) discloses a method for toughening and modifying polypropylene, which is characterized by comprising the following components in parts by weight: a. drying polypropylene (PP), elastomer (POE), ultra-high molecular weight polyethylene (UHMWPE) and low-density linear polyethylene (LLDPE) resin at the temperature of 60-80 ℃, and mixing the PP: POE: UHMWPE: mixing LLDPE (linear low density polyethylene) in a mass ratio of 100: 3-25: 2-15: 5-20 in a high-speed stirrer to obtain a raw material A; b. adding a stabilizer and a lubricant into the raw material A, wherein the mass ratio of polypropylene: a stabilizer: the lubricant is 100:0.2:1, and is stirred and mixed at high speed to obtain a raw material B; c. and extruding the raw material B by double screws, controlling the temperature of a processing section at 160-210 ℃, and controlling the rotating speed of the screws at 120-180 rpm to obtain the toughened and modified polypropylene, wherein the cantilever beam impact strength of the toughened and modified polypropylene can be improved by 13 times at most, and the tensile yield strength is reduced by no more than 12%. The method has relatively complex process and is not suitable for industrial mass production.
CN102977456B (application No. 201210523848.3) discloses a polypropylene toughening modifier and a polypropylene modified product thereof, which are the following components in percentage by weight: 15-50 wt.% of polyethylene, 15-50 wt.% of polypropylene, 20-55 wt.% of ethylene-octene copolymer, 0.1-2.0 wt.% of initiator F, and 0.05-1.0 wt.% of antioxidant. The polypropylene modified pipe and the injection molding product prepared by the polypropylene toughening modifier are prepared by physically mixing 2-15 wt.% of the polypropylene toughening modifier with 85-98 wt.% of polypropylene resin, extruding the polypropylene modified pipe on a single-screw pipe extruding machine set by using a proper amount of colorant, and injection molding the polypropylene modified product on an injection molding machine. The impact strength of the polypropylene modified product is improved by 28-34.5%, the melting temperature of the polypropylene modified product is increased by 1.5-1.8 ℃, and the crystallinity of the polypropylene modified product is increased by 26.7-35.2%. Can effectively reduce the slow secondary crystallization phenomenon in the later storage process of the polypropylene modified product and greatly eliminate the residual internal stress of the polypropylene modified product. The invention adopts the mixed polypropylene toughening modifier to be physically mixed with the polypropylene resin, so that the polypropylene performance is often influenced by uneven mixing, and the industrial batch production is difficult to realize.
CN106479037A (application No. 201510532426.6) discloses a method for toughening polypropylene, which comprises the following steps of firstly, preparing a toughening agent branched polyethylene thermoplastic elastomer and polypropylene according to the mass ratio of (5-20): (95-80), mixing in an internal mixer at the temperature of 150-220 ℃, wherein the rotating speed is 30-60 rpm, and the time is 5-30 min to prepare a premix; adding a stabilizer and a lubricant into the premix, and further mixing for 5-30 min; and finally, carrying out double-screw extrusion and granulation to obtain a finished product of the toughened polypropylene. The branched polyethylene thermoplastic elastomer adopted in the invention has the number average molecular weight of 10000-600000, the molecular weight distribution of 2.0-4.0 and the branching degree of 40-80/1000C. The method has simple process, and the obtained toughened polypropylene can improve the impact strength by 5-13 times and reduce the tensile strength by less than 10 percent and can be used for film materials and mould pressing materials. However, the method needs the processes of mixing by an internal mixer, adding a stabilizer and a lubricant, and the like, has complex process and is not suitable for industrial mass production.
The invention patent of CN 107459706A (application number 201710480923.5) discloses a polypropylene toughening modification process, belonging to the technical field of chemical industry, comprising the following steps: (1) polyolefin elastomer treatment, (2) mixture preparation, and (3) mixture extrusion molding. The technology effectively improves the physical and chemical properties of the polypropylene under the combined action of the modified polyolefin elastomer and various hosts, can obviously improve the impact strength and the rigidity of the polypropylene, can improve the tensile yield strength by more than 5 percent, greatly expands the application range of the polypropylene and has high economic value. However, the method needs polyolefin elastomer treatment, has relatively complex process, is not suitable for industrial mass production, and has the defects of uneven material mixing and influence on PP performance.
Disclosure of Invention
In order to solve the problems in the prior art and meet the requirement of hot forming product enterprises on the toughness of raw materials, the invention provides a preparation method of toughened polypropylene resin, which aims to improve the impact strength of the polypropylene resin, solve the problem that the application of polypropylene raw materials is limited at low temperature, particularly in winter and in refrigerators, and further widen the application range and the field of the polypropylene resin.
The technical scheme of the invention is as follows:
a preparation method of toughened polypropylene resin comprises the following steps:
1) taking liquid propylene as a raw material, adding ethylene with the mass percent of 0.8-1.4% of propylene by adopting an NDQ catalyst, and producing a random copolymerization polypropylene base resin with the molecular weight distribution of 5.0-7.5 in a single-ring pipe polypropylene device;
2) 95-85 parts of random copolymerization polypropylene base resin is selected, 5-15 parts of ultra-low density polyethylene resin is added, 0.05 part of antioxidant 1010, 0.1 part of antioxidant 168, 0.05 part of calcium stearate and 0.05 part of stearic acid monoglyceride, (1R, 2R, 3S, 4S) -rel-bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid disodium salt (HPN-20E) is added, and the mixture is further added, wherein 0.025-0.1 part of (1R, 2R, 3S, 4S) -rel-bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid disodium salt is added; and extruding and granulating by a double-screw extruder to obtain a toughened polypropylene product.
The purity of the liquid propylene is preferably more than or equal to 99.6 percent.
The purity of the ethylene is preferably more than or equal to 99.95 percent.
The single loop pipe is preferably a Spheripol process single loop pipe.
The ratio of the NDQ catalyst to the polypropylene is preferably 1 g: 19 to 33 Kg.
The ultra-low density polyethylene resin has the melt flow rate of 0.8-1.2g/10min and the density of less than 0.915g/cm3。
The toughened polypropylene resin prepared by the method of the invention; the molecular weight distribution Mw/Mn is 5.0-7.5; the melt flow rate is 0.8-2.0 g/10min under the conditions of 230 ℃ and 2.16Kg of load; the impact strength (23 ℃) of the notch of the simply supported beam is more than or equal to 4.5KJ/m2(ii) a The impact strength of the notch of the simply supported beam is more than or equal to 1.0KJ/m (-20 ℃), and the impact strength of the notch is more than or equal to 1.0KJ/m2。
The temperature of the twin-screw extruder used in the step 2) from feeding to a machine head is set as follows: 190-200 deg.C, 192-202 deg.C, 195-205 deg.C, 200-210 deg.C, 205-215 deg.C, 200-210 deg.C, 195-205 deg.C, 190-200 deg.C, 185-195 deg.C.
The molecular weight distribution Mw/Mn of the toughened polypropylene resin prepared by the method is 5.0-7.5; the melt flow rate is 0.8-2.0 g/10min under the conditions of 230 ℃ and 2.16Kg of load; the impact strength (23 ℃) of the notch of the simply supported beam is more than or equal to 4.5KJ/m2(ii) a The impact strength of the notch of the simply supported beam is more than or equal to 1.0KJ/m (-20 ℃), and the impact strength of the notch is more than or equal to 1.0KJ/m2。
The toughened polypropylene resin produced by the method can be processed into sheets, and the sheets meet the requirements of thermoforming use, particularly the requirements of negative pressure blister.
The toughened polypropylene resin produced by the method can be applied to the realization of industrial production of a Spheripol process single-ring-pipe polypropylene device of LBI company, and has the characteristics of simple process operation and controllable polymer performance index.
The toughened polypropylene resin produced by adopting the preparation method and the optimized formula has high melting sag resistance and excellent impact resistance, particularly the notch impact strength of the simple beam at normal temperature can be obviously improved by more than 30 percent compared with the common polypropylene, and the toughened polypropylene resin can be directly used for vacuum negative pressure plastic forming without adding other auxiliary materials, and is suitable for processing and producing the packaging of trays, meal covers, food packaging containers, folding boxes, stationery, industrial parts and the like for plastic forming.
Detailed Description
Example 1
1. Taking liquid propylene with the purity of 99.6 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 19Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.96 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. to 95 parts of a random copolymerized polypropylene extrusion resin, 5 parts of a melt flow rate of 0.8g/10min and a density of 0.915g/cm were added3Adding auxiliary agents into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, and the stearic acid monoglyceride is 0.0 part5 parts of HPN-20E, 0.025 parts of HPN-20E, fully mixing, and extruding by a double-screw extruder, wherein the temperatures of the extruder from feeding to a machine head are respectively as follows: granulating at 190 deg.C, 192 deg.C, 195 deg.C, 200 deg.C, 205 deg.C, 200 deg.C, 195 deg.C, 190 deg.C, 185 deg.C to obtain toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 2
1. Taking liquid propylene with the purity of 99.7 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 20Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.95 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. to 90 parts of a polypropylene random copolymer base resin, 10 parts of a melt flow rate of 0.9g/10min and a density of 0.913g/cm were added3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.025 part, fully mixing, and then extruding by using a double-screw extruder, wherein the temperature of the extruder from feeding to a machine head is respectively as follows: 192 ℃, 196 ℃, 203 ℃, 206 ℃, 208 ℃, 201 ℃, 195 ℃, 191 ℃ and 186 ℃ to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 3
1. Taking liquid propylene with the purity of 99.8 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 21Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.97 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. adding 15 parts of random copolymerization polypropylene base resin into 85 parts of random copolymerization polypropylene base resin, wherein the melt flow rate is 1.0g/10min, and the density is 0.914g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part,0.05 part of stearic acid monoglyceride and 0.025 part of HPN-20E, and after fully mixing, extruding by a double-screw extruder, wherein the temperatures of the extruder from feeding to a machine head are respectively as follows: 196 ℃, 197 ℃, 198 ℃, 203 ℃, 209 ℃, 202 ℃, 198 ℃, 193 ℃ and 188 ℃ for granulation, thus obtaining the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 4
1. Taking liquid propylene with the purity of 99.9 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 22Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.98 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. 95 parts of a polypropylene random copolymer base resin was added with 5 parts of a melt flow rate of 1.1g/10min and a density of 0.912g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.1 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 196 ℃, 199 ℃, 205 ℃, 206 ℃, 208 ℃, 203 ℃, 197 ℃, 196 ℃ and 189 ℃ for granulation, thus obtaining the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 5
1. Taking liquid propylene with the purity of 99.9 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 23Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.99 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. adding 10 parts of random copolymerization polypropylene base resin into 90 parts of the mixture, wherein the melt flow rate is 1.2g/10min, and the density is 0.910g/cm3Adding 0.05 part of antioxidant 1010 and 168 parts of antioxidant into the ultra-low density polyethylene resin0.1 part of calcium stearate, 0.05 part of stearic acid monoglyceride and 0.1 part of HPN-20E, wherein the components are fully mixed and then extruded by a double-screw extruder, and the temperature of the extruder from feeding to a machine head is respectively as follows: 193 ℃, 195 ℃, 197 ℃, 203 ℃, 206 ℃, 207 ℃, 202 ℃, 196 ℃, 193 ℃ and 188 ℃ and obtaining the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 6
1. Taking liquid propylene with the purity of 99.8 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 24Kg polypropylene/g catalyst), adding ethylene with the purity of 99.96 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. adding 15 parts of random copolymerization polypropylene base resin into 85 parts of random copolymerization polypropylene base resin, wherein the melt flow rate is 1.2g/10min, and the density is 0.906g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.1 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 191 ℃, 193 ℃, 196 ℃, 201 ℃, 206 ℃, 201 ℃, 196 ℃, 191 ℃ and 186 ℃ and granulating to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 7
1. Taking liquid propylene with the purity of 99.7 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 25Kg of polypropylene/g catalyst), adding ethylene with the purity of 99.97 percent and the mass percent of propylene of 1.4 percent, and producing the polypropylene random copolymer base resin on a single-ring pipe polypropylene device in the Spheripol process;
2. 95 parts of a polypropylene random copolymer base resin was added with 5 parts of a melt flow rate of 1.1g/10min and a density of 0.900g/cm3Ultra-low density polyethylene resin, and adding auxiliary agent, wherein the antioxidant1010 of 0.05 part, antioxidant 168 of 0.1 part, calcium stearate of 0.05 part, glycerol monostearate of 0.05 part and HPN-20E of 0.025 part, fully mixing, and extruding by a double-screw extruder, wherein the temperature of the extruder from feeding to a machine head is respectively as follows: 194 ℃, 193 ℃, 195 ℃, 207 ℃, 210 ℃, 209 ℃, 201 ℃, 205 ℃, 192 ℃ and 185 ℃ for granulation, thus obtaining the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 8
1. Taking liquid propylene with the purity of 99.6 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 26Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.98 percent and the mass percent of propylene of 1.4 percent, and producing the polypropylene random copolymer base resin on a single-ring pipe polypropylene device in the Spheripol process;
2. to 90 parts of a polypropylene random copolymer base resin, 10 parts of a polypropylene random copolymer resin having a melt flow rate of 1.0g/10min and a density of 0.899g/cm were added3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.025 part, fully mixing, and then extruding by using a double-screw extruder, wherein the temperature of the extruder from feeding to a machine head is respectively as follows: 198 deg.C, 195 deg.C, 199 deg.C, 201 deg.C, 207 deg.C, 210 deg.C, 199 deg.C, 195 deg.C, 189 deg.C, and granulating to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 9
1. Taking liquid propylene with the purity of 99.8 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 27Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.99 percent and the mass percent of propylene of 1.4 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. to 85 parts of a polypropylene random copolymer base resin, 15 parts of a polypropylene random copolymer resin having a melt flow rate of 0.9g/10min and a density of 0.895g/cm were added3Ultra-low density polyethylene resinAnd then adding an auxiliary agent, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.025 part, fully mixing, and extruding by using a double-screw extruder, wherein the temperature of the extruder from feeding to a machine head is respectively as follows: granulating at 190 ℃, 193 ℃, 195 ℃, 204 ℃, 209 ℃, 204 ℃, 195 ℃, 193 ℃ and 190 ℃ to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 10
1. Taking liquid propylene with the purity of 99.6 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 28Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.99 percent and the mass percent of propylene of 1.4 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. 95 parts of a polypropylene random copolymer base resin was added with 5 parts of a melt flow rate of 0.8g/10min and a density of 0.891g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.1 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 199 deg.C, 192 deg.C, 195 deg.C, 210 deg.C, 215 deg.C, 210 deg.C, 200 deg.C, 190 deg.C, 185 deg.C, granulating to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 11
1. Taking liquid propylene with the purity of 99.7 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 29Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.98 percent and the mass percent of propylene of 1.4 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. 95 parts of a polypropylene random copolymer base resin was added with 5 parts of a melt flow rate of 1.0g/10min and a density of 0.896g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.1 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 195 deg.C, 197 deg.C, 200 deg.C, 205 deg.C, 210 deg.C, 205 deg.C, 200 deg.C, 195 deg.C, 190 deg.C, granulating to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 12
1. Taking liquid propylene with the purity of 99.9 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 30Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.97 percent and the mass percent of propylene of 1.4 percent, and producing the polypropylene random copolymer base resin on a single-ring pipe polypropylene device in the Spheripol process;
2. to 85 parts of a polypropylene random copolymer base resin, 15 parts of a polypropylene random copolymer resin having a melt flow rate of 1.1g/10min and a density of 0.899g/cm were added3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.1 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 196 ℃, 199 ℃, 200 ℃, 209 ℃, 212 ℃, 208 ℃, 196 ℃, 193 ℃ and 185 ℃ for granulation, thus obtaining the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 13
1. Taking liquid propylene with the purity of 99.9 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 31Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.96 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. melt flow of 10 parts to 90 parts of a random copolymerized polypropylene base resinThe speed is 1.0g/10min, and the density is 0.902g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.03 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 198 deg.C, 201 deg.C, 206 deg.C, 209 deg.C, 210 deg.C, 205 deg.C, 196 deg.C, 192 deg.C, 187 deg.C, and granulating to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 14
1. Taking liquid propylene with the purity of 99.6 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 32Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.96 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. to 90 parts of a polypropylene random copolymer base resin, 10 parts of a polypropylene random copolymer resin having a melt flow rate of 0.8g/10min and a density of 0.904g/cm were added3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.04 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 195 deg.C, 199 deg.C, 200 deg.C, 208 deg.C, 215 deg.C, 213 deg.C, 210 deg.C, 205 deg.C, 200 deg.C, 195 deg.C, and granulating to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 15
1. Taking liquid propylene with the purity of 99.7 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 33Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.98 percent and the mass percent of propylene of 0.8 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. at 90 parts of random copolymerized polypropylene base10 parts of base resin are added, the melt flow rate is 1.0g/10min, and the density is 0.903g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.05 part, fully mixing, extruding by a double-screw extruder, and respectively adding the materials into a machine head at the following temperatures: 198 ℃, 199 ℃, 200 ℃, 202 ℃, 205 ℃, 203 ℃, 198 ℃, 190 ℃ and 189 ℃ and granulating to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 16
1. Taking liquid propylene with the purity of 99.8 percent as a main raw material, adopting an NDQ catalyst (the catalyst activity is 28Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.99 percent and the mass percent of propylene of 1.1 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. adding 6 parts of random copolymerization polypropylene base resin into 94 parts of polypropylene base resin, wherein the melt flow rate is 0.9g/10min, and the density is 0.911g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.03 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: granulating at 200 ℃, 201 ℃, 203 ℃, 205 ℃, 209 ℃, 215 ℃, 210 ℃, 195 ℃, 190 ℃ and 185 ℃ to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 17
1. Taking liquid propylene with the purity of 99.9 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 30Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.96 percent and the mass percent of propylene of 1.1 percent, and producing the polypropylene random copolymer base resin on a single-ring pipe polypropylene device in the Spheripol process;
2. 91 parts of a random copolymerized polypropylene base resin, 9 parts of a melt flow rate of 1.1g/10min and a density of 0.908g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.03 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 190 ℃, 192 ℃, 199 ℃, 200 ℃, 210 ℃, 215 ℃, 210 ℃, 195 ℃, 193 ℃ and 190 ℃ to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 18
1. Taking liquid propylene with the purity of 99.7 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 32Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.99 percent and the mass percent of propylene of 1.1 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. to 86 parts of a polypropylene random copolymer base resin, 14 parts of a polypropylene random copolymer resin having a melt flow rate of 1.0g/10min and a density of 0.910g/cm were added3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.03 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 191 ℃, 194 ℃, 195 ℃, 209 ℃, 210 ℃, 209 ℃, 199 ℃, 193 ℃ and 186 ℃ to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 19
1. Taking liquid propylene with the purity of 99.6 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 22Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.98 percent and the mass percent of propylene of 1.1 percent, and producing the polypropylene random copolymer base resin on a single-ring pipe polypropylene device in the Spheripol process;
2. to 94 parts of a polypropylene random copolymer base resin, 6 parts of a polypropylene random copolymer resin having a melt flow rate of 0.8g/10min and a density of 0.904g/cm were added3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.07 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: granulating at 200 ℃, 202 ℃, 205 ℃, 209 ℃, 210 ℃, 215 ℃, 210 ℃, 195 ℃, 193 ℃ and 190 ℃ to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 20
1. Taking liquid propylene with the purity of 99.8 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 24Kg polypropylene/g catalyst), adding ethylene with the purity of 99.97 percent and the mass percent of propylene of 1.1 percent, and producing the polypropylene random copolymer base resin on a Spheripol process single-ring pipe polypropylene device;
2. 91 parts of a random copolymerized polypropylene base resin, 9 parts of a melt flow rate of 1.2g/10min and a density of 0.913g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.07 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: 199 ℃, 201 ℃, 202 ℃, 205 ℃, 210 ℃, 211 ℃, 205 ℃, 200 ℃, 198 ℃ and 185 ℃ for granulation, thus obtaining the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Example 21
1. Taking liquid propylene with the purity of 99.7 percent as a main raw material, adopting an NDQ catalyst (the activity of the catalyst is 26Kg of polypropylene/g of catalyst), adding ethylene with the purity of 99.98 percent and the mass percent of propylene of 1.1 percent, and producing the polypropylene random copolymer base resin on a single-ring pipe polypropylene device in the Spheripol process;
2. to 86 parts of a polypropylene random copolymer base resin, 14 parts of a polypropylene random copolymer resin having a melt flow rate of 1.0g/10min and a density of 0.905g/cm3Adding an auxiliary agent into the ultra-low density polyethylene resin, wherein the antioxidant 1010 is 0.05 part, the antioxidant 168 is 0.1 part, the calcium stearate is 0.05 part, the stearic acid monoglyceride is 0.05 part, and the HPN-20E is 0.07 part, fully mixing, extruding by a double-screw extruder, and respectively setting the temperature of the extruder from feeding to a machine head as follows: granulating at 200 ℃, 202 ℃, 205 ℃, 210 ℃, 215 ℃, 210 ℃, 205 ℃, 200 ℃ and 195 ℃ to obtain the toughened polypropylene resin. The performance test was performed according to the national standard, and the results are shown in the molecular weight distribution test results and the mechanical property test results after the examples.
Molecular weight distribution test results:
Figure BDA0002252518120000121
Figure BDA0002252518120000131
the mechanical property test result is as follows:
Figure BDA0002252518120000132
Figure BDA0002252518120000141
in all the embodiments listed in the invention, the molecular weight distribution of the toughened polypropylene resin is more than or equal to 5.2, and compared with the common polypropylene with the same melt index, the processability is obviously improved; the impact strength of the notch of the normal-temperature simply supported beam is more than or equal to 5.59KJ/m2Compared with common polypropylene, the polypropylene composite material can be obviously improved by more than 30 percent, and the toughness of the resin is obviously improved. The toughened polypropylene resin can be directly used for vacuum negative pressure plastic molding without adding other auxiliary materials, and is used for processing and producing packaging of trays, meal covers, food packaging containers, folding boxes, stationery, industrial parts and the like.

Claims (8)

1. A preparation method of toughened polypropylene resin is characterized by comprising the following steps:
1) taking liquid propylene as a raw material, adding ethylene with the mass percent of 0.8-1.4% of propylene by adopting an NDQ catalyst, and producing a random copolymerization polypropylene base resin with the molecular weight distribution of 5.0-7.5 in a single-ring pipe polypropylene device;
2) 95-85 parts of random copolymerization polypropylene base resin is selected, 5-15 parts of ultra-low density polyethylene resin is added, 0.05 part of antioxidant 1010, 0.1 part of antioxidant 168, 0.05 part of calcium stearate and 0.05 part of stearic acid monoglyceride, (1R, 2R, 3S, 4S) -rel-bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid disodium salt (HPN-20E) is added, and the mixture is further added, wherein 0.025-0.1 part of (1R, 2R, 3S, 4S) -rel-bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid disodium salt is added; and extruding and granulating by a double-screw extruder to obtain a toughened polypropylene product.
2. The process as claimed in claim 1, wherein the liquid propylene has a purity of > 99.6%.
3. The process as claimed in claim 1, wherein the ethylene purity is > 99.95%.
4. The method of claim 1, wherein the single loop tube is a Spheripol process single loop tube.
5. The process of claim 1, wherein the ratio of NDQ catalyst to polypropylene is 1 g: 19 to 33 Kg.
6. The process of claim 1 wherein the ultra low density polyethylene resin has a melt flow rate of 0.8 to 1.2g/10min and a density of less than 0.915g/cm3。
7. The method as set forth in claim 1, wherein the twin-screw extruder used in the step 2) is set such that the temperature from the feeding to the head is set to: 190-200 deg.C, 192-202 deg.C, 195-205 deg.C, 200-210 deg.C, 205-215 deg.C, 200-210 deg.C, 195-205 deg.C, 190-200 deg.C, 185-195 deg.C.
8. The toughened polypropylene resin as claimed in claim 1, wherein the molecular weight distribution Mw/Mn is 5.0 to 7.5; the melt flow rate is 0.8-2.0 g/10min under the conditions of 230 ℃ and 2.16Kg of load; the impact strength (23 ℃) of the notch of the simply supported beam is more than or equal to 4.5KJ/m2(ii) a The impact strength of the notch of the simply supported beam is more than or equal to 1.0KJ/m (-20 ℃), and the impact strength of the notch is more than or equal to 1.0KJ/m2。
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