CN112080100B - High melt strength polypropylene and preparation method and application thereof - Google Patents
High melt strength polypropylene and preparation method and application thereof Download PDFInfo
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- CN112080100B CN112080100B CN201910508027.4A CN201910508027A CN112080100B CN 112080100 B CN112080100 B CN 112080100B CN 201910508027 A CN201910508027 A CN 201910508027A CN 112080100 B CN112080100 B CN 112080100B
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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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
- C08L2203/14—Applications used for foams
Abstract
The invention provides a high melt strength polypropylene and a preparation method and application thereof. According to the invention, special short-chain branch maleic anhydride is introduced into a polypropylene molecular chain as an active group, and the anhydride group on the short-chain branch reacts with alcoholic hydroxyl in a polyol molecule to graft the polyol to form a three-dimensional network structure, so that the polypropylene with high melt strength is prepared, and the polypropylene also has excellent mechanical properties such as tensile strength, bending strength and the like. The invention creatively takes maleic anhydride grafted polypropylene as a matrix, takes short-chain branch maleic anhydride in a molecular chain as an active group, makes the maleic anhydride react with alcoholic hydroxyl in a polyol molecule, and prepares melt strength polypropylene by changing a linear polypropylene structure; the method is carried out under mild conditions, has low reaction temperature and short reaction time, and avoids the degradation of the molecular weight of the polypropylene caused by high temperature so as to influence the mechanical properties of the product and the like.
Description
Technical Field
The invention relates to the technical field of polypropylene, in particular to high melt strength polypropylene and a preparation method and application thereof.
Background
Polypropylene is one of the most widely used and rapidly growing thermoplastic resins at present, and is widely applied to industries such as packaging, light industry, building, electronics, electric appliances, automobiles and the like due to the properties of low density, high melting point, heat resistance, corrosion resistance and the like. In general, polypropylene resins produced industrially have a polypropylene content of isotactic structure of about 95%. However, isotactic polypropylene molecules are linear structures and show relatively narrow molecular weight distribution, so that the isotactic polypropylene has low melt strength and poor sag resistance, thereby limiting the application of the isotactic polypropylene in the fields of foaming and thermoforming. In the hot forming production processes such as injection, extrusion, calendering and the like, the phenomena of curling and shrinking of the edge of a product can occur, and the defects of unstable size, uneven thickness and the like are caused. Therefore, it is necessary to prepare polypropylene with high melt strength.
In order to solve the problem, the linear structure of polypropylene must be changed into a long branched chain structure, so that the increase of viscosity can be effectively reduced while the melt strength is improved, and the processability of the polymer is still good. The current methods for preparing high melt strength polypropylene are mainly four: (1) the direct polymerization method is to add diene and other cross-linking agents into the propylene polymerization process to prepare the polypropylene with the long-chain branched structure, and because the method is implemented in the polymerization stage, the polymerization condition is harsh, and the branched structure is uncontrollable; (2) the radiation crosslinking method is that under the action of high-energy rays, alpha methyl on a polypropylene molecular chain loses one hydrogen atom to form high-activity tertiary carbon free radicals for degradation and crosslinking reaction, the linear structure of the polypropylene is converted into a long-chain branched structure, and the high-melt-strength polypropylene is prepared; the method has the disadvantages that the method is not suitable for crosslinking with thicker materials, easily causes polypropylene degradation, and has higher production cost; (3) the chemical crosslinking method is to mix polypropylene, initiator, antioxidant and multifunctional monomer to produce free radical reaction, and to connect polypropylene chains to form branched structure to prepare high melt strength polypropylene. The method has the characteristics of low cost, wide application range and the like, and is widely applied to preparing the polypropylene with high melt strength. But the problems that the branched chain structure of polypropylene is difficult to accurately control, functional monomers are remained, and toxic and harmful gases or peculiar smell is easy to generate exist; (4) the blending modification method is a simple and effective way at present. The melt strength of polypropylene is increased by adding a high melt strength polymer, rubber elastomer or filler to the polypropylene. However, the mechanical properties of polypropylene are reduced by adding blends to polypropylene, usually because polypropylene is not well compatible with the blends.
Disclosure of Invention
In order to improve the disadvantages of the prior art, the present invention provides a polypropylene composition comprising the following components:
(a) maleic anhydride grafted polypropylene; (b) a polyol; and (c) an antioxidant.
According to the invention, the polypropylene composition comprises the following components in parts by mass:
(a) 100 parts of maleic anhydride grafted polypropylene; (b) 1-50 parts of polyhydric alcohol; (c) 0.01-5 parts of antioxidant.
Illustratively, the polyol is present in 1 part, 2 parts, 3 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts by mass.
Illustratively, the antioxidant is 0.01 part, 0.02 part, 0.05 part, 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts by mass.
Preferably, the polypropylene composition comprises the following components in parts by mass:
(a) 100 parts of maleic anhydride grafted polypropylene; (b) 2-10 parts of polyhydric alcohol; (c) 0.1-1.5 parts of antioxidant.
Illustratively, the polyol is present in an amount of 2 parts, 3 parts, 4 parts, 5 parts, or 10 parts by mass.
Illustratively, the antioxidant is 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, 1.2 parts or 1.5 parts by mass.
Illustratively, the polypropylene composition comprises the following components in parts by mass:
(a) 100 parts of maleic anhydride grafted polypropylene; (b) 10 parts of polyol; (c) 0.5 part of antioxidant.
According to the invention, the maleic anhydride grafted polypropylene can be selected from powder and/or granules; when the concrete selection is carried out, the whole system is adapted; the polypropylene in the maleic anhydride grafted polypropylene can be homo-polypropylene or co-polypropylene; the maleic anhydride grafted polypropylene can be selected from commercially available products or prepared by methods known in the art, and the skilled person can select commercially available products or prepare the polypropylene by himself or herself according to production cost and production scale.
According to the invention, the grafting rate of the maleic anhydride grafted polypropylene can be selected from 0.005-10%, and the preferable grafting rate is 0.1-3%; illustratively, the grafting rate is 0.005%, 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%; the grafting rate in the optional range can ensure a branched chain structure, so that the prepared polypropylene has excellent processing performance and mechanical property, when the grafting rate is higher than 10%, the prepared polypropylene has high gel content, is not beneficial to processing and has poor mechanical property, and when the grafting rate is less than 0.005%, the mechanical property and the processing performance of the prepared polypropylene are not obviously changed compared with those of pure polypropylene.
According to the invention, the melt index of the maleic anhydride grafted polypropylene is 10-600 g/10min, and preferably the melt index is 10-300 g/10 min; illustratively, the melt index is 10g/10min, 15g/10min, 20g/10min, 30g/10min, 40g/10min, 50g/10min, 60g/10min, 80g/10min, 100g/10min, 150g/10min, 200g/10min, 250g/10min, 300g/10min, 350g/10min, 400g/10min, 450g/10min, 500g/10min, 600g/10 min; the melt index in the optional range can ensure that the weight average molecular weight of the polypropylene does not obviously decrease, so that the prepared polypropylene has excellent mechanical property, when the melt index is higher than 600g/10min, the molecular weight of the prepared polypropylene is very low, so that the mechanical property is poor, and when the melt index is lower than 10g/10min, the mechanical property of the prepared polypropylene is not obviously changed compared with that of pure polypropylene.
According to the invention, the polyol is selected from one or more of polymer polyols such as polyethylene glycol, polyvinyl alcohol, and the like, or monomeric polyols; illustratively, the polyethylene glycol is selected from polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 8000, polyethylene glycol 10000; the monomeric polyols are, for example, ethanol, glycerol, dipentaerythritol.
According to the invention, the antioxidant is at least one of hindered phenol antioxidant, amine antioxidant and phosphorus antioxidant, preferably hindered phenol antioxidant, and more preferably hindered phenol antioxidant is one or two of antioxidant 1010, antioxidant 1076, antioxidant B900, antioxidant 264, antioxidant 186 and antioxidant 2264.
The invention also provides a preparation method of the polypropylene composition, which comprises the following steps:
and mixing the maleic anhydride grafted polypropylene, the polyhydric alcohol and the antioxidant to prepare the polypropylene composition.
According to the invention, the mixing is carried out under stirring conditions, for example under mechanical stirring. The mixing temperature is 10-60 ℃, and the mixing time is 10min-1 h.
The invention also provides polypropylene, and the raw materials for preparing the polypropylene comprise the polypropylene composition.
According to the invention, the polypropylene is prepared from the polypropylene composition.
According to the invention, the polypropylene has a three-dimensional network-like structure.
According to the invention, the melt strength of the polypropylene is more than 900Pa.s, the tensile strength is more than 35MPa, the bending strength is more than or equal to 1000MPa, and the melt index is 0.25-8g/10 min.
The invention also provides a preparation method of the polypropylene, which comprises the following steps:
mixing maleic anhydride grafted polypropylene, polyhydric alcohol and an antioxidant, and reacting to prepare the polypropylene.
According to the invention, the method further comprises the steps of:
the product obtained from the reaction is washed to remove unreacted materials, for example, unreacted polyol. The removal of the unreacted polyhydric alcohol can effectively avoid the problems of environmental pollution and the like caused by the overflowing of the polyhydric alcohol in the use process of the product.
According to the invention, the reaction is preferably carried out in a twin-screw extruder; the reaction temperature is 150-230 ℃, and preferably 175-200 ℃; the reaction time is 1-10 min, preferably 3-5 min.
The invention also provides the use of the polypropylene, which is used in the fields of foaming and thermoforming.
The invention has the beneficial effects that:
the invention provides a high melt strength polypropylene and a preparation method and application thereof. According to the invention, special short-chain branch maleic anhydride is introduced into a polypropylene molecular chain as an active group, and the anhydride group on the short-chain branch reacts with alcoholic hydroxyl in a polyol molecule to graft the polyol to form a three-dimensional network structure, so that the polypropylene with high melt strength is prepared, and the polypropylene also has excellent mechanical properties such as tensile strength, bending strength and the like.
The invention creatively takes maleic anhydride grafted polypropylene as a matrix, takes short-chain branch maleic anhydride in a molecular chain as an active group, makes the maleic anhydride react with alcoholic hydroxyl in a polyol molecule, and prepares the high-melt-strength polypropylene by changing a linear polypropylene structure; according to the invention, the non-toxic and easily water-soluble polyol is selected, and the unreacted polyol can be removed by washing with water, so that the problems of residual functional monomers, easy generation of toxic and harmful gases or peculiar smell, generation of waste water after product post-treatment and the like in the traditional chemical crosslinking method are avoided; the method is carried out under mild conditions, has low reaction temperature and short reaction time, and avoids the degradation of the molecular weight of the polypropylene caused by high temperature so as to influence the mechanical property and the like of the product; the polyol used in the invention is liquid at the selected reaction temperature, can be fully contacted with the solid maleic anhydride grafted polypropylene, and is beneficial to synthesizing high-quality products. And the maleic anhydride grafted polypropylene is cheap and easy to obtain, and industrial products with different grafting rates can be purchased on the market.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The polypropylene (PP) raw material (ungrafted polypropylene) used in the following examples was a homopolypropylene powder having an average particle diameter of <0.06mm and a melt index of 9g/10 min.
The commercially available graft product 1 used in the examples described below was designated GPM200A, the grafting yield was 0.92% and the melt index was 160g/10 min.
The commercially available graft product 2 used in the examples described below was designated GPM200CH, the grafting yield was 1.92% and the melt index was 150g/10 min.
In order to illustrate various properties of the polypropylene with high melt strength prepared by the invention, the performance test is carried out, and the test method comprises the following steps:
and testing the tensile property by adopting a microcomputer-controlled electronic universal testing machine, wherein the tensile rate is 50mm/min according to the reference standard GB/T1040.1-2006.
The melt mass flow rate (MFR, unit: g/10min) was tested according to the reference standard GB/T3682-2000 at 230 ℃ under a load of 2.16 kg.
Melt strength (MS, unit: Pa · S) test: the prepared polypropylene was charged into a cylinder at a temperature of 230 ℃ and held at a constant temperature for 4min by means of a melt mass flow rate meter, and then a sample was extruded through a 2.095mm neck ring die under a load of 2.16kg, and the MFR of the corresponding sample was calculated in accordance with the following formula:
wherein Δ L-the length of the extruded specimen at 50% reduction in diameter, mm; r is0Radius, mm, at which the extruded bars initially emerge from the die.
Preparation example 1
Weighing 100g of polypropylene powder, placing the polypropylene powder in a closed reaction kettle, vacuumizing and filling nitrogen for three times to ensure that the reaction is carried out in the nitrogen atmosphere, dissolving 0.5g of grafting monomer maleic anhydride and 0.5g of initiator TBPB in 20mL of dimethylbenzene, adding the mixture into the reaction kettle, and stirring and swelling for about 0.5h at normal temperature. Heating to 120 ℃ for reaction for 3h to obtain PP grafted maleic anhydride, and performing Soxhlet extraction on the product by using acetone for 6h to purify the product to obtain purified maleic anhydride grafted polypropylene. The corresponding graft ratios were found to be 0.005, respectively, and the melt index was 9.5g/10 min.
Preparation example 2
The preparation method of preparation example 1 above was used, except that maleic anhydride-grafted polypropylene with different grafting ratios and melt indices was prepared by adjusting the amount of monomer maleic anhydride added, the amount of initiator added and the reaction temperature. The experimental conditions and test results of preparation examples 1 to 7 are shown in Table 1
Example 1
(1) And (4) premixing. 100 parts of the maleic anhydride-grafted polypropylene prepared in preparation example 3, 2.5 parts of PEG having a number average molecular weight of 600g/mol, and 0.5 part of a mixture of antioxidant 1010 and antioxidant 186 (mixed in a mass ratio of 1: 2) were put into a 500ml flask, and heated in an oil bath at 30 ℃ and mechanically stirred and mixed for 10 minutes.
(2) Solid phase grafting. Transferring the mixture in the step (1) into a double-screw extruder, and reacting for 5min at the temperature of 190 ℃;
(3) and washing the prepared product with water to remove unreacted PEG600, and drying in vacuum to obtain the high-melt-strength polypropylene.
Examples 2 to 13
The preparation method of example 1 above was employed except that polypropylene having different graft ratios, the kind of polyol, the amount of polyol added and the extrusion temperature in the twin-screw extruder were changed to prepare polypropylene having high melt strength.
Comparative examples 1 to 5
The method of preparation of example 1 above was used except that ungrafted polypropylene was used instead of maleic anhydride grafted polypropylene.
The experimental conditions and results of examples 1-13 and comparative examples 1-5 are shown in Table 2.
The preparation raw materials also comprise 0.5 part of antioxidant, which is a mixture of antioxidant 1010 and antioxidant 186 with the mass ratio of 1: 2.
It can be seen from the above examples and comparative examples that, the maleic anhydride grafted polypropylene of the present invention is grafted with polyol to form a three-dimensional network structure by reacting the anhydride groups on the short chain branches with the alcoholic hydroxyl groups in the polyol molecules, thereby obtaining polypropylene with high melt strength, while the polypropylene prepared without mixing the maleic anhydride grafted polypropylene with the polyol molecules has low melt strength and poor mechanical properties.
As can be seen from the comparison of example 1 and example 2, the mechanical properties and melt strength of the product are significantly improved as the amount of PEG added is increased. As can be seen from the above examples 2 and 5, the high temperature is advantageous in improving the melt strength, tensile strength and bending strength. From the comparison of example 3, example 5 and example 6 above, it can be seen that the grafting rate of maleic anhydride has an effect on the melt strength and mechanical properties of the product, and as the grafting rate increases, the melt strength and tensile strength of the product increase. As can be seen from the comparison of example 3, example 4, example 7, example 8 and example 9 above, the melt strength and tensile strength of the prepared product increased with increasing PEG molecular weight. The high melt strength propylene polymer material prepared by the invention is suitable for the fields of foaming, thermoforming, extrusion coating of a film blow molding machine and the like.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (19)
1. The polypropylene composition comprises the following components in parts by mass:
(a) 100 parts of maleic anhydride grafted polypropylene; (b) 2-10 parts of polyhydric alcohol; (c) 0.1-1.5 parts of antioxidant; the grafting rate of the maleic anhydride grafted polypropylene is 0.1-1.92%; the melt index of the maleic anhydride grafted polypropylene is 10-300 g/10 min; the polypropylene composition has a three-dimensional network-like structure.
2. The polypropylene composition according to claim 1, comprising the following components in parts by mass:
(a) 100 parts of maleic anhydride grafted polypropylene; (b) 10 parts of polyol; (c) 0.5 part of antioxidant.
3. The polypropylene composition according to any one of claims 1-2, wherein the polyol is selected from one or more of a polymer polyol or a monomer polyol.
4. The polypropylene composition according to claim 3, said polymer polyol being polyethylene glycol or polyvinyl alcohol.
5. The polypropylene composition according to claim 4, wherein said polyethylene glycol is selected from the group consisting of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 8000, polyethylene glycol 10000.
6. The polypropylene composition according to claim 3, wherein the monomeric polyol is glycerol, dipentaerythritol.
7. The polypropylene composition according to any one of claims 1-2, wherein the antioxidant is at least one of hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants.
8. The polypropylene composition according to claim 4, wherein the antioxidant is a hindered phenolic antioxidant.
9. The polypropylene composition according to claim 8, wherein the hindered phenolic antioxidant is one or two of 1010, 1076, B900, 264, 186 and 2264.
10. A process for the preparation of a polypropylene composition according to any one of claims 1 to 9, wherein the process comprises:
mixing maleic anhydride grafted polypropylene, polyhydric alcohol and an antioxidant to prepare the polypropylene composition; the mixing is carried out under the condition of stirring, the mixing temperature is 10-60 ℃, and the mixing time is 10min-1 h.
11. A process for the preparation of the polypropylene composition according to claim 10, wherein the stirring is performed under mechanical stirring.
12. A polypropylene, wherein a starting material for the preparation of said polypropylene comprises the polypropylene composition according to any one of claims 1 to 9.
13. The polypropylene according to claim 12, which is prepared from the polypropylene composition according to any one of claims 1 to 9.
14. A process for the preparation of polypropylene according to claim 12 or 13, comprising the steps of:
mixing maleic anhydride grafted polypropylene, polyhydric alcohol and an antioxidant, and reacting to prepare the polypropylene.
15. The method of claim 14, wherein the method further comprises the steps of:
washing the product obtained by the reaction to remove unreacted materials.
16. The method of claim 14, further comprising removing unreacted polyol.
17. The method of claim 14, the reacting being carried out in a twin screw extruder; the reaction temperature is 150-230 ℃, and the reaction time is 1-10 min.
18. The method according to claim 17, wherein the reaction temperature is 175-200 ℃, and the reaction time is 3-5 min.
19. Use of the polypropylene according to any one of claims 12 or 13 in the field of foaming and thermoforming.
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