CN109438602B - High-melt-strength polypropylene resin special for plastic suction molding and preparation method thereof - Google Patents
High-melt-strength polypropylene resin special for plastic suction molding and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high melt strength polypropylene resin special for plastic suction molding and a preparation method thereof, wherein the preparation method comprises the following steps: taking liquid propylene as a main raw material, adopting an NDQ catalyst with wide molecular weight distribution, and adding comonomer ethylene to a single-ring pipe polypropylene device in a Spheripol process to produce a random copolymerization polypropylene base resin with wide molecular weight distribution, wherein the activity of the catalyst is more than 30Kg of polypropylene/g of catalyst; and adding an auxiliary agent system, mixing by a mixer, extruding by a double-screw extruder, cooling, granulating, and drying granules to obtain the special polypropylene resin for plastic molding of the product. The molecular weight distribution Mw/Mn is 5.0-7.5; the melt flow rate is 0.8-2.0 g/10 min; the melt strength is more than 0.5N; the method has the characteristics of good processing fluidity, low processing temperature, high melt strength, good rebound resilience, high molding efficiency, high transparency, meeting the sanitary performance requirements of FDA, plasticizer and the like.
Description
Technical Field
The invention discloses a preparation method of a special polypropylene resin for high melt strength plastic suction molding, which is a method for preparing the special polypropylene resin for high melt strength plastic suction molding by taking liquid propylene with the purity of more than 99.7 percent as a main raw material, adding comonomer ethylene on a single-ring pipe polypropylene device in a Spheripol process by adopting a wide molecular weight distribution NDQ catalyst to produce a random copolymerization polypropylene base resin with wider molecular weight distribution (Mw/Mn is 5.0-7.5), adding an auxiliary agent system, fully mixing, extruding by a double-screw extruder, cooling and granulating, and drying granules to obtain the special polypropylene resin for high melt strength plastic suction 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. With the progress of polypropylene production technology, particularly the use of high-efficiency catalysts, the performance of polypropylene resin is continuously improved, and the application field of the polypropylene resin is continuously expanded, however, the softening point of the polypropylene with a linear structure is very close to the melting point of the polypropylene obtained by propylene polymerization with a Z-N catalyst and a metallocene catalyst, and the melt strength of the polypropylene is rapidly reduced after the melting point is exceeded, so that the defects of low melt strength and poor sag resistance of the polypropylene are caused. The melt does not exhibit a strain hardening effect on elongational flow, which directly causes some defects in the melt processing of polypropylene, sagging and local thinning upon thermoforming. Due to the defects, the application of polypropylene in the fields of plastic sucking molding, blow molding, foaming and other molding processing is severely limited. Therefore, improving the melt strength of polypropylene has been an important issue in the development of new products of polypropylene.
In recent years, the packaging amount of domestic transparent plastic-suction forming water cups, food trays and electronic and electric appliances is increased year by year, the annual demand of polypropylene exceeds 20 ten thousand tons, and part of downstream product manufacturers adopt the plastic-suction forming process and have higher requirements on the melt-sag resistance of sheets. In the downstream product industry, a method for improving the sag resistance of a sheet by adding 30% of HDPE into common polypropylene is adopted, but the method causes the problems of uneven mixing, reduced product rigidity, limited thermal deformation temperature, high cost and the like; the demand of downstream manufacturers for polypropylene raw materials with high sag resistance and suitable rigidity and toughness balance performance is increasingly urgent. The development of a new product of the polypropylene special material for high melt strength plastic uptake molding can further meet the requirements of users, improve the added value of the product, form differentiation and serialization of polypropylene thermal molding products, and realize customized production and service of target users. The research and development of the high melt strength plastic uptake molding polypropylene resin are more and more paid more attention by petrochemical enterprises.
The molecular structure of a polymer is a major factor affecting the melt strength of the polymer. In the case of polypropylene, the melt strength is mainly determined by the molecular weight, the molecular weight distribution and whether or not there is a long-chain branched structure in the molecular chain. The introduction of long chain branches into the carbon skeleton of polypropylene is most effective in improving the melt strength of polypropyleneThe method of (1). The direct polymerization process is the main way for preparing polypropylene with high melt strength in modern industry. China petrochemical and land refining chemical company uses a second-generation loop reactor (Spheripol process) of China petrochemical engineering construction company to produce high melt strength homo-polypropylene with the brand name of HMS 20Z. The process adopts the specific technology of the Chinese petrochemical Beijing chemical research institute, and utilizes different H in two serially connected reaction kettles2Concentration, HMSPP resins with broad relative molecular mass distribution were prepared. The MFR of the resin is about 2.2g/10min, the content of volatile organic compounds is low, the hygienic performance can meet the requirement of hygienic standards of the resin for food packaging, and the resin can be widely applied to the fields of foaming, thermoforming, film blowing, extrusion coating and the like.
At present, for the research and application of the polypropylene resin special for the high melt strength plastic suction molding, the patent and the literature are few. Such as: the invention of publication No. CN101724111A (application No. 200810224868.4) discloses a method for preparing broad molecular weight distribution polypropylene and its polymer, which comprises polymerizing propylene in the presence of a catalyst comprising the reaction product of: (1) at least one solid catalyst component comprising magnesium, titanium, halogen and at least two electron donors a and b, wherein the electron donor a is selected from a diol ester compound; the electron donor compound b is selected from mono-or multi-element aliphatic carboxylic ester, aromatic carboxylic ester or diether compound; the weight ratio of the electron donor compound a to the electron donor compound b is 2-80; (2) an alkyl aluminum compound; (3) optionally, an external electron donor component. The propylene polymer has the advantages of wide molecular weight distribution, high isotacticity and the like, and the preparation method is simple to operate.
The invention patent of publication No. CN1560093A (application No. 200410014194.7) discloses a method for preparing polypropylene with wide molecular weight distribution, which is an improved HYPOL polypropylene production process developed by three-well oiling, a flash tank is added in a liquid-phase polymer D-202 and a gas-phase polymerization kettle D-203, an improved production device is adopted to carry out a multi-kettle sectional polymerization method, the first-stage liquid-phase bulk polymerization is carried out at 40-70 ℃ to generate polypropylene with high or ultrahigh molecular weight, and the second-stage gas-phase polymerization is carried out at 70-90 ℃ and the hydrogen volume ratio concentration is 0.5-30% to generate the polypropylene with low molecular weight. The polypropylene contains a certain amount of high molecular weight polypropylene, has higher rigidity and melt strength, better fluidity and heat distortion temperature, and better molding processability. Can be used in the occasions requiring higher rigidity of polypropylene.
The invention patent of publication No. CN103589064B discloses preparation of a homo-polypropylene resin with a wider molecular weight distribution, which is characterized in that a base resin with a wider molecular weight distribution (Mw/Mn is 4.0-5.5) is produced on a Spheripol process single-ring pipe polypropylene device by adopting a catalyst with a wide molecular weight distribution, and then a homo-polypropylene resin is produced by adding a high-efficiency auxiliary agent system. The efficient assistant system is expressed by weight parts, the homo-polypropylene resin with wide molecular weight distribution is 100 parts, other assistants are 0.21-0.26 part, and the homo-polypropylene resin with wide molecular weight distribution is obtained by fully mixing the materials at a high speed, extruding by a double screw, cooling, granulating and drying granules. The homo-polypropylene resin with wider molecular weight distribution is easy to process, and the product is non-toxic and harmless, meets the environmental protection requirement, has excellent mechanical property, and is safe and sanitary.
The invention patent of application No. 201410345164.8 discloses 'a special resin for thermoforming random copolymerization polypropylene with wide molecular weight distribution and a preparation method thereof', the special resin has molecular weight distribution Mw/Mn of 5-7; the melt index is 3-7g/10 min. Ethylene is added to a single-ring pipe polypropylene device in a Spheripol process by adopting a Ziegler Natta NDQ catalyst, the activity of the NDQ catalyst is 21000-39000g of polypropylene/g of catalyst, the addition amount of the ethylene is 1.2-2.2 wt%, and the special random copolymerization polypropylene thermal forming resin is produced by adding an auxiliary additive system. The synthetic method of the special resin for the wide molecular weight distribution random copolymerization polypropylene thermal forming designed by the invention is applied to the realization of industrial production of the LBI public Spheripol technology single-ring pipe polypropylene device, and has the characteristics of simple technological operation and controllable polymer performance index.
The invention patent of application No. 201510487644.2 discloses 'a special resin for blow molding of random copolymerized polypropylene with low melting point and wide molecular weight distribution and a preparation method thereof', the resin is random copolymerized polypropylene with low melting point and wide molecular weight distribution, and the molecular weight distribution Mw/Mn is 5-7; the melt index is 1.0-4.0 g/10 min. A wide molecular weight distribution Ziegler-Natta (NDQ) catalyst is adopted and is arranged on a single-ring pipe polypropylene device of a Spheripol process. Ethylene is added, the NDQ activity is 21000-39000g of polypropylene/g of catalyst, the addition amount of the ethylene is 2.0-3.0% (wt), and an auxiliary additive system is added to produce the special resin for the blow molding of the random copolymer polypropylene with low melting index and wide molecular weight distribution, which is suitable for the processing requirements of an extrusion blowing method and the like. The preparation method is simple to operate. The product resin has good processing performance, meets the environmental protection requirement, has excellent mechanical property and transparency, and has been accepted by downstream enterprises.
The raw materials mentioned in the articles and patents cannot meet the use requirements of the existing thermoforming customers, namely meet the requirements of the thermoforming customers on single negative pressure blister, the invention provides a scheme for adjusting the structure and the performance of the resin raw materials by combining the use of catalysts, auxiliaries and processes, and develops the special polypropylene resin for high melt strength blister forming.
Disclosure of Invention
In order to meet the requirement of a client for hot forming and separate negative pressure plastic uptake use, a preparation method of a high melt strength special polypropylene resin for plastic uptake forming is designed, and particularly, a wide molecular weight distribution NDQ catalyst is adopted, liquid propylene with the purity of more than 99.7 percent is used as a main raw material on a single-ring pipe polypropylene device in a Spheripol process, a comonomer ethylene (the content is 1.0-1.4 percent) is added, a random copolymerization polypropylene base resin with a wide molecular weight distribution (Mw/Mn is 5.5-7.5) is produced, an auxiliary agent system is added, after full mixing, the random copolymerization polypropylene base resin is extruded by a double-screw extruder, cooled and cut into granules, and granules are dried, so that the high melt strength special polypropylene resin for plastic uptake forming is obtained.
The invention provides the following technical scheme
The invention prepares a high melt strength special polypropylene resin for plastic suction molding, the molecular weight distribution Mw/Mn of the high melt strength special polypropylene resin is 5.0-7.5; the melt flow rate is 0.8-2.0 g/10 min; fusion furnaceBulk strength > 0.5N; the impact strength (23 ℃) of the notch of the simply supported beam is more than or equal to 4.6KJ/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 invention relates to a preparation method of polypropylene resin special for high melt strength plastic uptake molding; the method comprises the following steps:
1) taking liquid propylene as a main raw material, adopting an NDQ catalyst with wide molecular weight distribution, and adding comonomer ethylene to a single-ring pipe polypropylene device in a Spheripol process to produce a random copolymerization polypropylene base resin with wide molecular weight distribution, wherein the activity of the catalyst is more than 30Kg of polypropylene/g of catalyst;
2) and adding an auxiliary agent system, mixing by a mixer, extruding by a double-screw extruder, cooling, granulating, and drying granules to obtain the special polypropylene resin for plastic molding of the product.
The purity of the main raw material liquid propylene is more than 99.7 percent;
the activity of the selected NDQ catalyst is 30-45Kg polypropylene/g catalyst;
the content of the added comonomer ethylene is 1.0-1.4%;
the assistant system is a combination of an antioxidant 1010, an antioxidant 168, calcium stearate, stearic acid monoglyceride and 1,2, 3-trideoxy-4, 6:5, 7-bis-O- [ (4-propylphenyl) methylene ] -nonanol in a ratio of 1:2:1:1: 0.5-1.0.
The mixing time of the mixer is 600r/min for 40-80 seconds, and the mixing time of the mixer is 2000r/min for 10-60 seconds.
The resin is extruded by a double-screw extruder, the rotating speed of a screw of the extruder is 60-600 r/min, and the temperature of the extruder from feeding to a machine head is set as follows: 190-.
The Spheripol process single-ring pipe adopts a Spheripol process single-ring pipe polypropylene device of LBI company.
The melt index under the conditions of 230 ℃ and 2.16Kg of load is 0.8-2.0 g/10 min.
The invention relates to a preparation method of a high melt strength special polypropylene resin for plastic suction molding, which adopts a wide molecular weight distribution NDQ catalyst, wherein the catalyst activity is more than 30Kg polypropylene/g catalyst, on a single-ring pipe polypropylene device of a Spheripol process, liquid propylene with the purity of more than 99.7 percent is used as a main raw material, comonomer ethylene (content is 1.0-1.4 percent) is added to produce a random copolymerization polypropylene base resin with wider molecular weight distribution, an auxiliary agent system is added, after full mixing, the random copolymerization polypropylene base resin is extruded by a double-screw extruder, cooled and granulated, and granules are dried to obtain the special polypropylene resin for plastic suction molding of the product. The special polypropylene resin for plastic molding has the characteristics of high transparency, high melt strength, good melt-out resistance, capability of meeting the use requirement of independent plastic molding of the PP resin and the like, and meanwhile, the product is non-toxic, harmless, safe and sanitary and meets the requirement of environmental protection.
The high melt strength polypropylene resin special for plastic molding has the characteristics of high transparency (haze is less than or equal to 10%), high melt strength, good melt-down resistance, excellent physical property and processability, capability of meeting the single plastic-molding use requirement of the PP resin and the like.
The special polypropylene resin for high melt strength plastic suction molding is 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 high melt strength polypropylene resin specially for plastic suction molding produced by the optimized formula of the preparation method has the characteristics of good processing fluidity, low processing temperature, high melt strength, good rebound resilience, high molding efficiency and high transparency, and meets the sanitary performance requirements of FDA, new national standards, plasticizers and the like. On the premise of keeping the same rigidity as the homopolymerization product, the high-toughness low-temperature-drop-resistant polypropylene composite material has the characteristics of high toughness, good low-temperature-drop resistance, capability of microwave heating and the like, is industrially produced at present, is accepted by thermoforming customers, and is used for producing various trays, meal covers, food packaging containers, folding boxes, stationery, industrial parts and the like through independent negative-pressure plastic uptake.
Detailed Description
Example 1:
in a Spheripol process single-ring pipe polypropylene device of LBI company, liquid propylene with the purity of 99.8 percent is used as a main raw material, a wide molecular weight distribution catalyst NDQ and the catalyst activity of 32Kg polypropylene/g catalyst are adopted, comonomer ethylene (the content is 1.0 percent) is added, random copolymerization polypropylene base resin with wider molecular weight distribution (Mw/Mn is 5.5-7.5) is produced, the melt index is 0.8-1.0 g/10min, a high-efficiency auxiliary agent system is added, the proportion of an antioxidant 1010, an antioxidant 168, calcium stearate, stearic acid monoglyceride and 1,2, 3-trideoxy-4, 6:5, 7-di-O- [ (4-propylphenyl) methylene ] -nonanol is 1:2:1:1:0.5-1.0, after full mixing, extruding, cooling and granulating by a double-screw extruder, and drying granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The efficient assistant system is represented by weight parts, wherein 100 parts of the raw material of the broad molecular weight distribution random copolymerization polypropylene resin and 0.275 parts of the assistant are added into a high-speed mixer for fully mixing, 40 seconds of mixing at 600r/min and 10 seconds of mixing at 2000r/min, and then the mixture is added into a double-screw extruder for granulation, and the temperature of the extruder from a feed inlet to each section of a machine head is 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. And drying the granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The resin is subjected to sample strip injection molding, a single-screw injection molding machine is adopted to perform sample strip injection molding testing, and the injection molding temperature is set as follows: 200 deg.C, 210 deg.C, 220 deg.C, 210 deg.C, 205 deg.C. The mechanical property test and microstructure characterization of the test sample strip according to the national standard are shown in tables 1 and 2.
Example 2:
in a Spheripol process single-ring pipe polypropylene device of LBI company, liquid propylene with the purity of 99.9 percent is used as a main raw material, a wide molecular weight distribution catalyst NDQ is adopted, the activity of the catalyst is 35Kg polypropylene/g catalyst, comonomer ethylene (the content is 1.4 percent) is added, random copolymerization polypropylene base resin with wider molecular weight distribution (Mw/Mn is 5.5-7.5) is produced, the melt index is 1.0-1.2 g/10min, a high-efficiency auxiliary agent system is added, the proportion of an antioxidant 1010, an antioxidant 168, calcium stearate, stearic acid monoglyceride and 1,2, 3-trideoxy-4, 6:5, 7-di-O- [ (4-propylphenyl) methylene ] -nonanol is 1:2:1:1:0.5-1.0, after full mixing, extruding, cooling and granulating by a double-screw extruder, and drying granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The efficient auxiliary agent system is represented by weight parts, wherein 100 parts of the raw material of the broad molecular weight distribution random copolymerization polypropylene resin and 0.280 part of the auxiliary agent are added into a high-speed mixer for fully mixing, 40 seconds of mixing is carried out at 600r/min, then 20 seconds of mixing is carried out at 2000r/min, then the mixture is added into a double-screw extruder for granulation, and the temperature of the extruder in the granulation process is measured from a feed inlet to each section of a machine head: 192 deg.C, 198 deg.C, 205 deg.C, 209 deg.C, 213 deg.C, 208 deg.C, 198 deg.C, 195 deg.C, and 191 deg.C. And drying the granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The resin is subjected to sample strip injection molding, a single-screw injection molding machine is adopted to perform sample strip injection molding testing, and the injection molding temperature is set as follows: 200 deg.C, 210 deg.C, 220 deg.C, 210 deg.C, 205 deg.C. The mechanical property test and microstructure characterization of the test sample strip according to the national standard are shown in tables 1 and 2.
Example 3:
in a Spheripol process single-ring pipe polypropylene device of LBI company, liquid propylene with the purity of 99.9 percent is used as a main raw material, a wide molecular weight distribution catalyst NDQ is adopted, the activity of the catalyst is 38Kg polypropylene/g catalyst, comonomer ethylene (the content is 1.1 percent) is added, random copolymerization polypropylene base resin with wider molecular weight distribution (Mw/Mn is 5.5-7.5) is produced, the melt index is 1.2-1.4 g/10min, a high-efficiency auxiliary agent system is added, the proportion of an antioxidant 1010, an antioxidant 168, calcium stearate, stearic acid monoglyceride and 1,2, 3-trideoxy-4, 6:5, 7-di-O- [ (4-propylphenyl) methylene ] -nonanol is 1:2:1:1:0.5-1.0, after full mixing, extruding, cooling and granulating by a double-screw extruder, and drying granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The efficient auxiliary agent system is represented by weight parts, wherein 100 parts of the raw material of the broad molecular weight distribution random copolymerization polypropylene resin and 0.285 part of the auxiliary agent are added into a high-speed mixer for fully mixing, 50 seconds are mixed at 600r/min and then 10 seconds are mixed at 2000r/min, and then the mixture is added into a double-screw extruder for granulation, and the temperature of the extruder in the granulation process is measured from a feed inlet to each section of a machine head: 191 deg.C, 197 deg.C, 198 deg.C, 206 deg.C, 213 deg.C, 215 deg.C, 203 deg.C, 199 deg.C, 197 deg.C, 186 deg.C. And drying the granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The resin is subjected to sample strip injection molding, a single-screw injection molding machine is adopted to perform sample strip injection molding testing, and the injection molding temperature is set as follows: 200 deg.C, 210 deg.C, 220 deg.C, 210 deg.C, 205 deg.C. The mechanical property test and microstructure characterization of the test sample strip according to the national standard are shown in tables 1 and 2.
Example 4:
in a Spheripol process single-ring pipe polypropylene device of LBI company, liquid propylene with the purity of 99.8 percent is used as a main raw material, a wide molecular weight distribution catalyst NDQ and the catalyst activity of 45Kg polypropylene/g catalyst are adopted, comonomer ethylene (the content is 1.2 percent) is added, random copolymerization polypropylene base resin with wider molecular weight distribution (Mw/Mn is 5.5 to 7.5) is produced, the melt index is 1.4 to 1.6g/10min, a high-efficiency auxiliary agent system is added, the proportion of an antioxidant 1010, an antioxidant 168, calcium stearate, stearic acid monoglyceride and 1,2, 3-trideoxy-4, 6:5, 7-di-O- [ (4-propylphenyl) methylene ] -nonanol is 1:2:1:1:0.5-1.0, after full mixing, extruding, cooling and granulating by a double-screw extruder, and drying granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The efficient auxiliary agent system is represented by weight parts, wherein 100 parts of the raw material of the broad molecular weight distribution random copolymerization polypropylene resin and 0.290 part of the auxiliary agent are added into a high-speed mixer for fully mixing, and are mixed for 60 seconds at a speed of 600r/min and then for 20 seconds at a speed of 2000r/min, and then are added into a double-screw extruder for granulation, and the temperature of the extruder from a feed inlet to each section of a machine head in the granulation process is as follows: 195 deg.C, 202 deg.C, 210 deg.C, 213 deg.C, 215 deg.C, 208 deg.C, 205 deg.C, 194 deg.C, 188 deg.C. And drying the granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The resin is subjected to sample strip injection molding, a single-screw injection molding machine is adopted to perform sample strip injection molding testing, and the injection molding temperature is set as follows: 200 deg.C, 210 deg.C, 220 deg.C, 210 deg.C, 205 deg.C. The mechanical property test and microstructure characterization of the test sample strip according to the national standard are shown in tables 1 and 2.
Example 5:
in a Spheripol process single-ring pipe polypropylene device of LBI company, liquid propylene with the purity of 99.9 percent is used as a main raw material, a wide molecular weight distribution catalyst NDQ is adopted, the activity of the catalyst is 40Kg polypropylene/g catalyst, comonomer ethylene (the content is 1.3 percent) is added, random copolymerization polypropylene base resin with wider molecular weight distribution (Mw/Mn is 5.5-7.5) is produced, the melt index is 1.6-1.8 g/10min, a high-efficiency auxiliary agent system is added, the proportion of an antioxidant 1010, an antioxidant 168, calcium stearate, stearic acid monoglyceride and 1,2, 3-trideoxy-4, 6:5, 7-di-O- [ (4-propylphenyl) methylene ] -nonanol is 1:2:1:1:0.5-1.0, after full mixing, extruding, cooling and granulating by a double-screw extruder, and drying granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The efficient auxiliary agent system is represented by weight parts, wherein 100 parts of the raw material of the broad molecular weight distribution random copolymerization polypropylene resin and 0.285 part of the auxiliary agent are added into a high-speed mixer for fully mixing, and are mixed for 80 seconds at a speed of 600r/min and then mixed for 10 seconds at a speed of 2000r/min, and then added into a double-screw extruder for granulation, and the temperature of the extruder in the granulation process is measured from a feed inlet to each section of a machine head: 192 deg.C, 195 deg.C, 202 deg.C, 207 deg.C, 212 deg.C, 208 deg.C, 202 deg.C, 193 deg.C, 190 deg.C. And drying the granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The resin is subjected to sample strip injection molding, a single-screw injection molding machine is adopted to perform sample strip injection molding testing, and the injection molding temperature is set as follows: 200 deg.C, 210 deg.C, 220 deg.C, 210 deg.C, 205 deg.C. The mechanical property test and microstructure characterization of the test sample strip according to the national standard are shown in tables 1 and 2.
Example 6:
in a Spheripol process single-ring pipe polypropylene device of LBI company, liquid propylene with the purity of 99.8 percent is used as a main raw material, a wide molecular weight distribution catalyst NDQ is adopted, the activity of the catalyst is 35Kg polypropylene/g catalyst, comonomer ethylene (the content is 1.4 percent) is added, random copolymerization polypropylene base resin with wider molecular weight distribution (Mw/Mn is 5.5-7.5) is produced, the melt index is 1.8-2.0 g/10min, a high-efficiency auxiliary agent system is added, the proportion of an antioxidant 1010, an antioxidant 168, calcium stearate, stearic acid monoglyceride and 1,2, 3-trideoxy-4, 6:5, 7-di-O- [ (4-propylphenyl) methylene ] -nonanol is 1:2:1:1:0.5-1.0, after full mixing, extruding, cooling and granulating by a double-screw extruder, and drying granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The efficient auxiliary agent system is represented by weight parts, wherein 100 parts of the raw material of the broad molecular weight distribution random copolymerization polypropylene resin and 0.300 part of the auxiliary agent are added into a high-speed mixer for fully mixing, 40 seconds of mixing is carried out at 600r/min, then 60 seconds of mixing is carried out at 2000r/min, then the mixture is added into a double-screw extruder for granulation, and the temperature of the extruder in the granulation process is measured from a feed inlet to each section of a machine head: 191 deg.C, 193 deg.C, 202 deg.C, 210 deg.C, 212 deg.C, 208 deg.C, 203 deg.C, 194 deg.C, 189 deg.C. And drying the granules to obtain the special polypropylene resin for high melt strength plastic molding of the product. The resin is subjected to sample strip injection molding, a single-screw injection molding machine is adopted to perform sample strip injection molding testing, and the injection molding temperature is set as follows: 200 deg.C, 210 deg.C, 220 deg.C, 210 deg.C, 205 deg.C. The mechanical property test and microstructure characterization of the test sample strip according to the national standard are shown in tables 1 and 2.
Table 1: molecular weight distribution and melt strength test results:
table 2: the mechanical property test result is as follows:
Claims (7)
1. the special polypropylene resin for high melt strength plastic uptake molding is characterized in that: the molecular weight distribution Mw/Mn is 5.0-7.5; the melt index measured under the conditions of 230 ℃ and 2.16Kg load is 0.8-2.0 g/10 min; the melt strength is more than 0.5N; the impact strength of the notch of the simply supported beam is more than or equal to 4.6KJ/m when the test is carried out at the temperature of 23 DEG C2(ii) a The impact strength of the notch of the simply supported beam is more than or equal to 1.0KJ/m when the temperature is measured at minus 20 DEG C2(ii) a The preparation method of the high melt strength polypropylene resin special for plastic suction molding comprises the following steps:
1) taking liquid propylene as a main raw material, adopting a wide molecular weight distribution NDQ catalyst, wherein the activity of the catalyst is more than 30Kg of polypropylene/g of catalyst, and adding 1.0-1.4% (wt) of comonomer ethylene on a single-ring pipe polypropylene device in a Spheripol process to produce a random copolymerization polypropylene base resin with the molecular weight distribution of 5.0-7.5;
2) and adding an auxiliary agent system, mixing by a mixer, extruding by a double-screw extruder, cooling, granulating, and drying granules to obtain the special polypropylene resin for plastic molding.
2. The resin according to claim 1, wherein the main raw material liquid propylene used has a purity of more than 99.7%.
3. The resin of claim 1, wherein the NDQ catalyst is selected to have an activity of 30 to 45Kg of polypropylene per gram of catalyst.
4. The resin of claim 1 wherein the adjuvant system is a combination of antioxidant 1010, antioxidant 168, calcium stearate, glycerol monostearate and 1,2, 3-trideoxy-4, 6:5, 7-bis-O- [ (4-propylphenyl) methylene ] -nonanol in a ratio of 1:2:1:1: 0.5-1.0.
5. The resin according to claim 1, wherein the mixing in the mixer is carried out at 600r/min for 40-80 seconds, and at 2000r/min for 10-60 seconds.
6. The resin according to claim 1, wherein the resin is extruded from a twin-screw extruder, the rotation speed of the extruder screw is 60 to 600r/min, and the temperature of the extruder from the feeding to the head is set as follows: 190-.
7. The resin according to claim 1, wherein the Spheripol process single loop pipe is a Spheripol process single loop pipe polypropylene device manufactured by LBI.
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| CN104558852A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| CN105585774A (en) * | 2015-12-25 | 2016-05-18 | 神华集团有限责任公司 | Homopolymerized transparent polypropylene composition |
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| CN104558852A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| CN106336475A (en) * | 2015-08-10 | 2017-01-18 | 中国石油化工股份有限公司 | Low-melting index and wide-molecular weight distribution polypropylene random copolymer resin specially used for blow molding, and production method of resin |
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| CN105754232A (en) * | 2016-03-29 | 2016-07-13 | 中国石油化工股份有限公司 | Heat-proof high-rigidity high-toughness transparent thermal-forming polypropylene material and preparation process thereof |
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