Polypropylene beta crystal compound additive easy to clean, low in residue and capable of inducing high content of beta crystal and preparation method of polypropylene beta crystal compound additive

Abstract

The invention relates to the technical field of polypropylene resin preparation, in particular to a polypropylene beta crystal compound additive easy to clean, low in residue and capable of inducing high content of beta crystals and a preparation method of the polypropylene beta crystal compound additive, and the polypropylene beta crystal compound additive is obtained by uniformly mixing a compound beta crystal nucleating agent, a compound beta crystal coating separant and a compound antioxidant in a high-speed mixer. According to the polypropylene beta crystal compound additive easy to clean, low in residue and capable of inducing the high content of beta crystals, the compound beta crystal nucleating agent is adopted, the induction rate of the beta crystals is increased, the coating separant is put forward and introduced for the first time, the main beta crystal coating separant and the auxiliary beta crystal coating separant are matched for use, the coating and isolating effects are achieved, and the high content of the beta crystals in the polypropylene beta crystal compound additive is improved. The composite coating separant and the composite beta crystal nucleating agent generate a synergistic effect, so that the content of the produced polypropylene beta crystal is high, the polypropylene beta crystal nucleating agent in an additive system and an extruder system is free of residues and easy to clean, and the subsequent production of polypropylene resin products is not influenced.

Description

Technical Field

[0001] The invention relates to the technical field of polypropylene resin preparation, and is a polypropylene beta crystal compound additive which is easy to clean, has low residue and can induce high beta crystal content, and a preparation method thereof. Background Art

[0002] Polypropylene (PP) is a general-purpose resin with large output, wide application, low price and easy access, and its development areas are very wide. Polypropylene is a complex polycrystalline polymer, which can generate five different forms of spherulite structures, namely α, β, γ, δ and quasi-crystalline, under different crystallization conditions. Under normal conditions, PP mainly crystallizes into α-crystal form, so commercial polypropylene is usually α-crystal PP. α-crystal belongs to the monoclinic system. The lamellar crystals in α-crystal form grow radially outward from the center of the spherulite. α-crystal PP has the advantages of good heat resistance, convenient processing, recyclability, and hot-melt connection, but its toughness is poor and needs to be improved. Compared with α-crystal PP, β-crystal is bundled or cabbage-shaped, that is, it is bundled in parallel from the center of the spherulite and then branched outward. β-crystal PP has good toughness and high heat deformation temperature, so it has received widespread attention, but β-crystal needs to be prepared under specific conditions and is not easy to obtain, so there are very few varieties of polypropylene resin with high β-crystal content.

[0003] The prior art is to obtain a polypropylene resin with a high β-crystal content by adding a polypropylene β-crystal nucleating agent. This approach brings about two seemingly irreconcilable phenomena: It is found through experiments that, first, currently, when the commercially available polypropylene β-crystal nucleating agent that can induce the production of a high content of β-crystals is used in a continuous production device, a large amount of residue will remain in the device additive system and the extruder system for a long time, causing great quality pollution to the subsequent production of other polypropylene resins. The pollution and residue last for a long time, the time and probability of the pollution are uncertain, and it is very difficult to clean, which will produce a large amount of waste, resulting in quality accidents and cost losses in the production device; second, the currently available commercially available non-polluting, low-residue polypropylene β-crystal nucleating agent cannot efficiently induce the production of a polypropylene resin with a high β-crystal content. The produced β-crystal polypropylene resin has a low β-crystal content, and the performance of the low β-crystal polypropylene resin is poor. Moreover, this commercially available non-polluting, low-residue polypropylene β-crystal nucleating agent cannot produce high-quality β-crystal polypropylene, cannot meet the needs of manufacturers, and is not suitable for use in production devices. Therefore, a polypropylene β-crystal nucleating agent system that can ensure a high content of polypropylene β-crystals, without pollution or residue in additives and extruder systems of industrial production equipment, and can quickly clean related systems in a short period of time has become a hot spot that needs to be urgently found in this field. Polypropylene β-crystal compound additives that can meet the above requirements and their preparation methods are the key core technologies for industrial-scale production of β-crystal polypropylene resins.

[0004] The Chinese patent document with publication number CN114773673A discloses an amide-type β-crystal nucleating agent and its application. The composition of the nucleating agent includes at least one of aromatic amide and aromatic amide salt, mainly highlighting the excellent β-crystal nucleating performance and the simple preparation process of the nucleating agent.

[0005] The Chinese patent document with the announcement number CN105061404B discloses an imide-based polypropylene β-crystal nucleating agent and a preparation method thereof. The nucleating agent has a general structural formula of formula I, wherein n=0 to 20, R1 is a nitro group, a hydroxyl group, an amino group, a halogen group or an alkyl group, R2 is selected from one of the following three groups: H, an alkyl group, a group containing a carboxyl group or a hydroxyl group or a halogen group or an aromatic heterocycle, and R3 is selected from one of the following three groups: H, an alkyl group, a group containing a carboxyl group or a hydroxyl group or a halogen group or an aromatic heterocycle.

[0006] The Chinese patent document with publication number CN104558847A discloses a homopolymer polypropylene β-crystal nucleating agent, which includes the following components calculated by mass percentage: 0.1% to 10% of a high-efficiency β-crystal nucleating agent, 1% to 5% of an acid absorber, 1% to 5% of a shape-attaching agent, 0% to 75% of rigid particles, and 30% to 90% of a synergist. It has the characteristics of high nucleation efficiency and low cost, and greatly improves the toughness of homopolymer polypropylene while maintaining the rigidity and elongation at break of homopolymer polypropylene.

[0007] The Chinese patent document with the announcement number CN103965545B discloses a polypropylene β-crystal nucleating agent composition and a preparation method thereof and a β-crystal polypropylene composition and a preparation method thereof. The polypropylene β-crystal nucleating agent composition contains a nucleating agent A and a nucleating agent B, wherein A is a carboxylate nucleating agent and B is an aromatic amide β-nucleating agent, and the weight ratio of A to B is 15:1 to 1:15. The nucleating agent can improve the comprehensive thermal and mechanical properties of the product material, and the preparation process is simple.

[0008] The Chinese patent document with the announcement number CN103539692B discloses a method for preparing an amide-based polypropylene β-crystal nucleating agent with p-phenylenediamine as the skeleton. The nucleating agent is specifically N-N'-1,4-phenylenedicyclohexylcarboxamide, which highlights that the raw materials of the nucleating agent are easily available and the process operation is simple.

[0009] The Chinese patent document with the announcement number CN103214736B discloses an amide-based β-crystal isotactic polypropylene nucleating agent and its preparation method and application. The process is simple, the raw materials and reagents used are cheap, the side reactions are few, and the β-crystal structure content in isotactic polypropylene is as high as 99%.

[0010] A Chinese patent document with publication number CN102558683A discloses a polypropylene β-crystal nucleating agent composition and its application. The composition is prepared by mixing barium tetrahydrophthalate, calcium tetrahydrophthalate and the like with auxiliary agents such as hydrotalcite or calcium carbonate in proportion, and the composition has better function than a single-component β-nucleating agent.

[0011] The Chinese patent document with publication number CN102226026B discloses a composite β-crystal nucleating agent for polypropylene processing. The composite β-crystal nucleating agent is composed of one or more β-crystal nucleating agents and one or more synergists, wherein the composition ratio (by mass) of the nucleating agent to the synergist is 100 parts of the nucleating agent and 0.0001 to 1000 parts of the synergist, preferably 1 to 200 parts. Due to the presence of the synergist, a series of high-efficiency and low-cost composite β-crystal nucleating agents can be obtained.

[0012] A Chinese patent document with publication number CN102040532B discloses a method for preparing a polypropylene β-crystal nucleating agent. The method comprises contacting a dicarboxylic acid with an amine in the presence of a catalyst and a solvent for condensation reaction, wherein the amine is a primary amine and / or a secondary amine, wherein the catalyst is one or more of phosphorus pentoxide, polyphosphoric acid and triphenyl phosphite, and the solvent is pyridine, and the molar ratio of the catalyst to the pyridine is 1:10 to 30.

[0013] Publication No. CN1966563B discloses a β-crystalline polypropylene nucleating agent and a crystalline polypropylene resin composition containing the nucleating agent. The β-crystalline nucleating agent is added to polypropylene and mixed. The addition method can be direct addition or preparation into a concentrated masterbatch. The dosage is 0.005% to 10% of the weight of PP. It can induce PP to produce a higher content of β-crystalline. The β-crystalline content calculated by the WAXD method can reach 90%, which can greatly improve the toughness and impact strength of homopolymer polypropylene. Compared with pure polypropylene, the improvement can reach more than 3 times.

[0014] Publication No. CN1304469C discloses a β-crystal nucleating agent and the resulting product, wherein the nucleating agent contains a rare earth organic complex formed by one or more rare earth elements or a plurality of organic compounds.

[0015] The above-mentioned prior art has three main problems: (1) The prior art discloses nucleating agents and their effects in polypropylene, covers a wide range of various nucleating agents, highlights the nucleation efficiency and β-crystal content, and discloses the excellent mechanical properties of β-crystalline polypropylene, but the β-crystalline nucleating agent formulas involved do not demonstrate the residual β-crystalline of polypropylene, the difficulty of cleaning, and whether it can be industrialized and continuously mass-produced while ensuring a high β-crystalline content of polypropylene; (2) The β-crystalline nucleating agent formula and preparation method of polypropylene disclosed in the prior art only highlight that the raw materials of the preparation method are easy to obtain, the process is simple, and the feasibility is strong, but most of them are single agents, and a small amount involves compounded nucleating agents. The compounding effect is not demonstrated, and there is no involvement of and β-crystal coated release agent; (3) The polypropylene β-nucleating agent involved in the prior art is only used for one of the homopolymer, block copolymer, and random copolymer polypropylenes, has no wide application effect, does not provide a matching antioxidant system additive, remains in small-scale or pilot tests, and has no industrial application implementation cases; (4) The industrial-scale production of polypropylene β-crystalline resin in the world's common process equipment (PP equipment of Basell, Bp, Exxon-Mobil, UCC, Dow, etc.) must face the problem of β-crystalline nucleating agent residue and cleaning cycle. The queried patents currently do not involve this problem, and there are no similar or similar patents for producing β-crystalline polypropylene resin in industrial continuous production equipment. Summary of the invention

[0016] The present invention provides a polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals and a preparation method thereof, which overcomes the deficiencies of the above-mentioned prior art and can effectively solve the problems that the existing polypropylene compound additive cannot ensure a high content of β-crystals and is easy to remain in the device and difficult to clean.

[0017] One of the technical solutions of the present invention is achieved through the following measures: a polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals, and the raw materials include 0.05 to 1 part of a composite β-crystal nucleating agent, 0.05 to 1 part of a composite β-crystal coating isolation agent and 0.01 to 2 parts of a composite antioxidant by weight.

[0018] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: The above-mentioned polypropylene β-crystal compound additive is easy to clean, has low residue and can induce high β-crystal content. The raw materials include 0.1 to 0.5 parts of composite β-crystal nucleating agent, 0.1 to 0.2 parts of composite β-crystal coating isolation agent and 0.1 to 0.5 parts of composite antioxidant in terms of weight.

[0019] The above-mentioned composite β-crystal nucleating agent includes 10% to 90% of a main β-crystal nucleating agent and the remainder of an auxiliary β-crystal nucleating agent by weight percentage, and is obtained by the following method: the required amount of the main β-crystal nucleating agent and the auxiliary β-crystal nucleating agent are placed in a high-speed mixer and mixed to obtain a composite β-crystal nucleating agent.

[0020] The main β-crystal nucleating agent is an aromatic amide compound, and the aromatic amide compound is N,N-dicyclohexylterephthalamide.

[0021] The auxiliary β-crystal nucleating agent is a carboxylate compound, and the carboxylate compound is a condensed ring supported sodium calcium pimelate.

[0022] The above-mentioned composite β-crystal coated separator comprises 1% to 99% of a main β-crystal coated separator and the remainder of an auxiliary β-crystal coated separator by weight percentage, and is obtained by the following method: the required amount of the main β-crystal coated separator and the auxiliary β-crystal coated separator are placed in a high-speed mixer and mixed to obtain a composite β-crystal coated separator.

[0023] The main β crystal coating isolation agent is β-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate.

[0024] The auxiliary β-crystal coating release agent is a polymer wax compound, and the polymer wax compound is one of vinyl polymer wax and propylene polymer wax.

[0025] The above-mentioned composite antioxidant is three or more of antioxidant 1010, antioxidant 168, antioxidant cast, antioxidant 626, antioxidant 1330 and antioxidant dgms.

[0026] The composite antioxidant is a mixture of 0.02 to 0.5 parts of antioxidant 1010, 0.02 to 0.5 parts of antioxidant 168 and 0.01 to 0.1 parts of antioxidant cast in parts by weight.

[0027] The composite antioxidant is a mixture of 0.02 to 0.5 parts of antioxidant 1010, 0.02 to 0.5 parts of antioxidant 168, 0.02 to 0.5 parts of antioxidant 626 and 0.01 to 0.1 parts of antioxidant dgms in parts by weight.

[0028] The composite antioxidant is a mixture of 0.02 to 0.5 parts of antioxidant 1010, 0.02 to 0.5 parts of antioxidant 168, 0.05 to 0.5 parts of antioxidant 1330 and 0.01 to 0.1 parts of antioxidant cast in parts by weight.

[0029] The above-mentioned polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystal is obtained according to the following method: the required amount of composite β-crystal nucleating agent, composite β-crystal coating isolation agent and composite antioxidant are placed in a high-speed mixer and mixed to obtain the polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystal.

[0030] The second technical solution of the present invention is achieved by the following measures: a method for preparing a polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals, which is carried out according to the following method: the required amount of composite β-crystal nucleating agent, composite β-crystal coating isolation agent and composite antioxidant are placed in a high-speed mixer and mixed to obtain a polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals.

[0031] The polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals not only adopts a compound β-crystal nucleating agent to increase the induction rate of β-crystals, but also proposes and introduces a coating release agent for the first time, and adopts a main β-crystal coating release agent + an auxiliary β-crystal coating release agent for use in combination to play a coating and isolation role. The composite coating release agent and the composite β-crystal nucleating agent produce a synergistic effect, so that the produced polypropylene has a high β-crystal content, and ensures that the polypropylene β-crystal nucleating agent in the additive system and the extruder system has no residue and is easy to clean, and has no influence on the production of subsequent polypropylene resin products. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is the XRD pattern of the homopolymer β-crystalline polypropylene resin prepared in Example 17 of the present invention.

[0033] Figure 2 This is the DSC graph of the homopolymer β-crystalline polypropylene resin prepared in Example 17 of the present invention.

[0034] Figure 3 This is the DSC graph of the impact-resistant copolymer β-crystalline polypropylene resin prepared in Example 18 of the present invention.

[0035] Figure 4 This is the DSC chart of the random copolymer β-crystalline polypropylene resin prepared in Example 19 of the present invention.

[0036] Figure 5 This is the DSC graph of the homopolymerized β-crystalline polypropylene resin prepared in Comparative Example 1 of the present invention.

[0037] Figure 6 This is the DSC graph of the impact-resistant copolymer β-crystalline polypropylene resin prepared in Comparative Example 2 of the present invention.

[0038] Figure 7 This is the DSC graph of the random copolymer β-crystalline polypropylene resin prepared in Comparative Example 3 of the present invention.

[0039] Figure 8 This is the XRD diagram of the β-crystalline polypropylene resin prepared in Example 17 and Comparative Examples 4 to 6 of the present invention. DETAILED DESCRIPTION

[0040] The present invention is not limited by the following embodiments, and specific implementation methods can be determined according to the technical scheme of the present invention and actual conditions. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all known and commonly used chemical reagents and chemicals in the prior art; the percentages in the present invention are all mass percentages unless otherwise specified.

[0041] The present invention will be further described below in conjunction with embodiments: Example 1: The polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals, comprises raw materials by weight including 0.05 to 1 part of a composite β-crystal nucleating agent, 0.05 to 1 part of a composite β-crystal coating isolation agent and 0.01 to 2 parts of a composite antioxidant.

[0042] Example 2: As an optimization of the above example, the polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals, comprises raw materials by weight including 0.1 to 0.5 parts of a composite β-crystal nucleating agent, 0.1 to 0.2 parts of a composite β-crystal coating isolation agent and 0.1 to 0.5 parts of a composite antioxidant.

[0043] Example 3: As an optimization of the above example, the composite β-crystal nucleating agent includes 10% to 90% of a main β-crystal nucleating agent and the remainder of an auxiliary β-crystal nucleating agent by weight, and is obtained by the following method: the required amount of the main β-crystal nucleating agent and the auxiliary β-crystal nucleating agent are placed in a high-speed mixer and mixed to obtain a composite β-crystal nucleating agent.

[0044] Example 4: As an optimization of the above example, the main β-crystal nucleating agent is an aromatic amide compound, and the aromatic amide compound is N,N-dicyclohexyl terephthalamide. Its structural formula is as follows: Example 5: As an optimization of the above example, the auxiliary β-crystal nucleating agent is a carboxylate compound, and the carboxylate compound is a condensed ring supported sodium calcium pimelate. Its specific structural formula is as follows: Example 6: As an optimization of the above example, the composite β-crystal coating isolation agent includes 1% to 99% of a main β-crystal coating isolation agent and the remainder of an auxiliary β-crystal coating isolation agent in weight percentage, and is obtained by the following method: the required amount of the main β-crystal coating isolation agent and the auxiliary β-crystal coating isolation agent are placed in a high-speed mixer and mixed to obtain a composite β-crystal coating isolation agent.

[0045] Example 7: As an optimization of the above example, the main β-crystal coating separator is β-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate. Its specific structural formula is as follows: Embodiment 8: As an optimization of the above embodiment, the auxiliary β-crystal coating isolation agent is a polymer wax compound, and the polymer wax compound is one of vinyl polymer wax and propylene polymer wax.

[0046] Example 9: As an optimization of the above example, the composite antioxidant is three or more of the antioxidant 1010, antioxidant 168, antioxidant cast, antioxidant 626, antioxidant 1330, and antioxidant dgms.

[0047] Example 10: As an optimization of the above example, the composite antioxidant is a mixture of 0.02 to 0.5 parts by weight of antioxidant 1010, 0.02 to 0.5 parts by weight of antioxidant 168, and 0.01 to 0.1 parts by weight of antioxidant cast.

[0048] The composite antioxidant of Example 10 of the present invention is used in the production of homopolymerized β-crystalline polypropylene resin products.

[0049] Example 11: As an optimization of the above example, the composite antioxidant is a mixture of 0.02 to 0.5 parts by weight of antioxidant 1010, 0.02 to 0.5 parts by weight of antioxidant 168, 0.02 to 0.5 parts by weight of antioxidant 626, and 0.01 to 0.1 parts by weight of antioxidant dgms.

[0050] The composite antioxidant of Example 11 of the present invention is used in the production of impact-resistant copolymer β-crystalline polypropylene resin products.

[0051] Example 12: As an optimization of the above example, the composite antioxidant is a mixture of 0.02 to 0.5 parts by weight of antioxidant 1010, 0.02 to 0.5 parts by weight of antioxidant 168, 0.05 to 0.5 parts by weight of antioxidant 1330, and 0.01 to 0.1 parts by weight of antioxidant cast.

[0052] The composite antioxidant of Example 12 of the present invention is used in the production of random copolymer β-crystalline polypropylene resin products.

[0053] Example 13: As an optimization of the above example, the polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals is obtained by the following method: the required amount of composite β-crystal nucleating agent, composite β-crystal coating isolation agent and composite antioxidant are placed in a high-speed mixer and mixed to obtain a polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals.

[0054] Embodiment 14: The polypropylene beta crystal compound additive which is easy to clean, has low residue and can induce a high content of beta crystals, comprises raw materials by weight including 0.05 parts of a composite beta crystal nucleating agent (10% by weight of dicyclohexyl parabenzeline aromatic amide and the balance of condensed ring supported calcium sodium pimelate), 0.05 parts of a composite beta crystal coating separator (1% by weight of beta-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and the balance of vinyl polymer wax) and 0.05 parts of a composite antioxidant (a mixture of 0.02 parts of antioxidant 1010, 0.02 parts of antioxidant 168 and 0.01 parts of antioxidant cast), and is obtained by the following method: required amounts of the composite beta crystal nucleating agent, the composite beta crystal coating separator and the composite antioxidant are placed in a high-speed mixer and mixed to obtain the polypropylene beta crystal compound additive which is easy to clean, has low residue and can induce a high content of beta crystals.

[0055] Embodiment 15: The polypropylene beta crystal compound additive which is easy to clean, has low residue and can induce a high content of beta crystals, comprises raw materials by weight including 1 part of a composite beta crystal nucleating agent (90% by weight of dicyclohexyl parabenzamide and the remainder of condensed ring supported calcium sodium pimelate), 1 part of a composite beta crystal coating separator (99% of beta-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and the remainder of propylene polymer wax) and 1.6 parts of a composite antioxidant (a mixture of 0.5 parts of antioxidant 1010, 0.5 parts of antioxidant 168, 0.5 parts of antioxidant 626 and 0.1 parts of antioxidant dgms), and is obtained by the following method: required amounts of the composite beta crystal nucleating agent, the composite beta crystal coating separator and the composite antioxidant are placed in a high-speed mixer and mixed to obtain the polypropylene beta crystal compound additive which is easy to clean, has low residue and can induce a high content of beta crystals.

[0056] Embodiment 16: The polypropylene beta crystal compound additive which is easy to clean, has low residue and can induce a high content of beta crystals, comprises raw materials by weight including 0.5 parts of a composite beta crystal nucleating agent (50% by weight of dicyclohexyl parabenzene aromatic amide and the remainder of condensed ring supported calcium sodium pimelate), 0.5 parts of a composite beta crystal coating separator (50% of beta-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and the remainder of vinyl polymer wax) and 0.35 parts of a composite antioxidant (a mixture of 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 168, 0.1 parts of antioxidant 1330 and 0.05 parts of antioxidant cast), and is obtained by the following method: required amounts of the composite beta crystal nucleating agent, the composite beta crystal coating separator and the composite antioxidant are placed in a high-speed mixer and mixed to obtain the polypropylene beta crystal compound additive which is easy to clean, has low residue and can induce a high content of beta crystals.

[0057] Compared with the prior art, the present invention has the following beneficial effects: First, the main β-crystal nucleating agent + auxiliary β-crystal nucleating agent are used together to greatly increase the induction rate of β-crystal; Secondly, the coating release agent was proposed and introduced for the first time, and the main β-crystal coating release agent + auxiliary β-crystal coating release agent were used together to play the role of coating and isolation. The coating release agent and the composite β-crystal nucleating agent produced a superposition effect of 1+1>2, which made the β-crystal content of the produced polypropylene high, and ensured that the β-crystal nucleating agent in the additive system and extruder system had no residue and was easy to clean, and had no impact on the production of subsequent polypropylene resin products.

[0058] Thirdly, the polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals has good universality and is suitable for polypropylene polymerization production devices of different processes. The polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals is used as a raw material to produce homopolymerization, impact copolymerization and random copolymerization β-crystal polypropylene resins without adding additional equipment or changing the existing production process. The conversion of different models is not affected by the residual polypropylene β-crystal nucleating agent. The production bottleneck of special materials for producing β-crystal homopolymerization, impact copolymerization and random copolymerization of polypropylene resins in domestic petrochemical plants is effectively solved, and β-crystal polypropylene products can be applied on a large scale.

[0059] The following is the application of the polypropylene β-crystal compound additive of the present invention which is easy to clean, has low residue and can induce high β-crystal content in the production of β-crystal polypropylene resin.

[0060] Embodiment 17: The homopolymerized β-crystalline polypropylene resin is obtained by the following method: the polypropylene β-crystalline compound additive which is easy to clean, has low residue and can induce a high content of β-crystalline prepared in Example 14 of the present invention is added to 100 parts of polypropylene resin powder and mixed evenly, and then extruded and granulated at 175° C. using a twin-screw extruder to obtain a homopolymerized β-crystalline polypropylene resin.

[0061] The homopolymerized β-crystalline polypropylene resin prepared in Example 17 of the present invention has a melt index of 0.2 g / 10 min, a tensile break nominal strain of 450%, and a simply supported beam impact strength of 98 kJ / m 2 , the heat deformation temperature is 107℃.

[0062] The homopolymerized β-crystalline polypropylene resin prepared in Example 17 of the present invention was subjected to XRD analysis, and the test results were as follows: Figure 1 As shown, 1 is the XRD pattern of the homopolymer β-crystalline polypropylene resin obtained by the first melt extrusion, 2 is the XRD pattern of the homopolymer β-crystalline polypropylene resin obtained by the second melt extrusion, and 3 is the XRD pattern of the homopolymer β-crystalline polypropylene resin obtained by the third melt extrusion after adding the masterbatch. Figure 1It can be seen that the β-crystal content measured by XRD is 82%, and the melting / crystallization analysis shows a double melting point. The homopolymer β-crystal polypropylene resin is melt-extruded for the second time by a twin-screw extruder, and the β-crystal content measured by XRD is 74%; all basic physical properties remain good; the homopolymer β-crystal polypropylene resin is melt-extruded for the third time with the addition of masterbatch, and the β-crystal content measured by XRD is 71%, and all basic physical properties remain good.

[0063] The homopolymerized β-crystalline polypropylene resin prepared in Example 17 of the present invention was subjected to DSC testing and analysis. The test results are as follows: Figure 2 As shown by Figure 2 It can be seen that after the first extrusion, the same homopolymer β-crystalline polypropylene resin was extruded again after cleaning for 6 hours. The melting peak showed a single peak and there was no double peak phenomenon, indicating that the residue had been cleaned and there was no residue.

[0064] Embodiment 18: The impact-resistant copolymer β-crystalline polypropylene resin is obtained by the following method: the polypropylene β-crystalline compound additive which is easy to clean, has low residue and can induce a high content of β-crystalline prepared in Example 15 of the present invention is added to 100 parts of polypropylene resin powder and mixed evenly, and then extruded and granulated at 250° C. using a twin-screw extruder to obtain the impact-resistant copolymer β-crystalline polypropylene resin.

[0065] The impact-resistant copolymer β-crystalline polypropylene resin prepared in Example 18 of the present invention has a melt index of 2.0 g / 10 min, a β-crystal content of 72% as measured by XRD, and a double melting point as determined by melt-crystallization analysis.

[0066] The impact-resistant copolymer β-crystalline polypropylene resin prepared in Example 18 of the present invention was subjected to DSC testing and analysis. The test results are as follows: Figure 3 As shown by Figure 3 It can be seen that after the first extrusion, the same impact-resistant copolymer β-crystalline polypropylene resin was extruded again after cleaning for 3.6 hours. There was no double peak, and its melting peak showed a single peak. There was no double peak phenomenon, indicating that the residue had been cleaned and there was no residue.

[0067] Embodiment 19: The random copolymer β-crystalline polypropylene resin is obtained by the following method: the polypropylene β-crystalline compound additive which is easy to clean, has low residue and can induce a high content of β-crystalline prepared in Example 16 of the present invention is added to 100 parts of polypropylene resin powder and mixed evenly, and then extruded and granulated at 200° C. using a twin-screw extruder to obtain a random copolymer β-crystalline polypropylene resin.

[0068] The random copolymer β-crystalline polypropylene resin prepared in Example 19 of the present invention has a melt index of 0.24 g / 10 min, a tensile break nominal strain of 570%, and a simply supported beam impact strength of 83 kJ / m 2 , heat deformation temperature is 77℃, its XRD measured β crystal content is 81%, and melting-crystallization analysis shows double melting points.

[0069] The random copolymer β-crystalline polypropylene resin prepared in Example 19 of the present invention was subjected to DSC detection and analysis. The detection results are as follows: Figure 4 As shown by Figure 4 It can be seen that after the first extrusion, the same random copolymer polypropylene is extruded again after cleaning for 3 hours without double peaks, and its melting peak shows a single peak without double peak phenomenon, indicating that the residue has been cleaned and there is no residue.

[0070] Comparative Example 1: The difference from Example 17 is that in the preparation method of the homopolymer β-crystalline polypropylene resin, the polypropylene β-crystalline compound additive that is easy to clean, has low residue and can induce a high content of β-crystals prepared in Example 14 of the present invention is modified to the existing compound additive model GYSY-2059.

[0071] The homopolymerized β-crystalline polypropylene resin prepared in Comparative Example 1 of the present invention has a melt index of 0.2 g / 10 min, a nominal strain at break of 400%, and a simply supported beam impact strength of 75 kJ / m 2 , heat deformation temperature 75℃, after XRD detection and analysis, the β-crystal content measured by XRD was 78%, the melt-crystallization analysis showed a double melting point, after the second melt extrusion by a twin-screw extruder, the β-crystal content measured by XRD was 24%; after the masterbatch was added and melted for the third time, the β-crystal content measured by XRD was 12%, and the basic physical properties were greatly reduced.

[0072] The homopolymerized β-crystalline polypropylene resin prepared in Comparative Example 1 of the present invention was subjected to DSC testing and analysis. The test results are as follows: Figure 5 As shown by Figure 5 It can be seen that after the first extrusion, the same homopolymer β-crystalline polypropylene resin was extruded again after cleaning for 10 hours, and its melting peak still had double peaks. The double peaks still appeared after 20 days of trial production on the industrial device. This shows that the residue cannot be cleaned in a short period of time, and the residue exists in various parts of the device for a long time.

[0073] Comparative Example 2: The difference from Example 18 is that in the preparation method of the impact-resistant copolymer β-crystalline polypropylene resin, the polypropylene β-crystalline compound additive that is easy to clean, has low residue and can induce a high content of β-crystals prepared in Example 15 of the present invention is modified to the existing compound additive model TMY-12.

[0074] The impact-resistant copolymer β-crystalline polypropylene resin prepared in Comparative Example 2 of the present invention was subjected to DSC testing and analysis. The test results are as follows: Figure 6 As shown by Figure 6 It can be seen that after the first extrusion, the same impact copolymer β-crystalline polypropylene resin was extruded again after cleaning for 48 hours, and its melting peak still had double peaks, indicating that the residue could not be quickly cleaned in a short time.

[0075] Comparative Example 3: The difference from Example 19 is that in the preparation method of the random copolymer β-crystalline polypropylene resin, the polypropylene β-crystalline compound additive that is easy to clean, has low residue and can induce a high content of β-crystals prepared in Example 16 of the present invention is modified to the existing compound additive model TMY-12.

[0076] The random copolymer β-crystalline polypropylene resin prepared in Comparative Example 3 of the present invention has a melt index of 0.24 g / 10 min, a nominal strain at break of 400%, and a simply supported beam impact strength of 75 kJ / m 2 , heat deformation temperature is 75℃, its XRD measured β crystal content is 78%, and melting-crystallization analysis shows double melting points.

[0077] The random copolymer β-crystalline polypropylene resin prepared in Comparative Example 3 of the present invention was subjected to DSC detection and analysis. The detection results are as follows: Figure 7 As shown by Figure 7 It can be seen that after multiple extrusions, a high content of β crystals can be maintained when external interference exists, and the mechanical properties imparted by β crystals can be maintained. After the first extrusion, the same random copolymer β crystal polypropylene resin was extruded again after cleaning for 30 hours and still had double peaks, indicating that the residue existed for a long time.

[0078] Comparative Example 4: The difference from Example 17 is that, in the preparation method of the homopolymer β-crystalline polypropylene resin, the polypropylene β-crystalline compound additive that is easy to clean, has low residue and can induce a high content of β-crystals prepared in Example 14 of the present invention is modified to an existing low-residue, easy-to-clean compound additive model NAA-89.

[0079] Comparative Example 5: The difference from Example 18 is that, in the preparation method of the impact-resistant copolymer β-crystalline polypropylene resin, the polypropylene β-crystalline compound additive that is easy to clean, has low residue and can induce a high content of β-crystals prepared in Example 15 of the present invention is modified to the existing low-residue, easy-to-clean compound additive model NAA-89.

[0080] Comparative Example 6: The difference from Example 19 is that, in the preparation method of the random copolymer β-crystalline polypropylene resin, the polypropylene β-crystalline compound additive that is easy to clean, has low residue and can induce a high content of β-crystals prepared in Example 16 of the present invention is modified to the existing low-residue, easy-to-clean compound additive model NAA-89.

[0081] The homopolymer β-crystalline polypropylene resin prepared in Example 17 of the present invention and Comparative Example 4, the impact-resistant copolymer β-crystalline polypropylene resin prepared in Comparative Example 5, and the random copolymer β-crystalline polypropylene resin prepared in Comparative Example 6 were subjected to XRD detection and analysis. The detection results are as follows: Figure 8 As shown, among which, Figure 8It can be seen that after the first extrusion, the cleaning is very fast for 3 to 4 hours, and there is no double peak phenomenon in the melting peak. However, the β-crystal content of the β-crystal polypropylene resin prepared in Comparative Examples 4 to 6 is very low, and it is easy to transform or disappear when there is external interference such as secondary melting or the addition of masterbatch, and its β-crystal content is less than 15%. The homopolymer β-crystal polypropylene resin prepared in Example 17 of the present invention has a β-crystal content of about 80% when there is external interference such as secondary melting or the addition of masterbatch. Figure 7 The mid-red peak is the highest.

[0082] In summary, it can be seen from the analysis results of Examples 17 to 19 of the present invention and Comparative Examples 1 to 3 that although the existing compound additives can ensure the β-crystal content in the β-crystal polypropylene resin product, it has serious residues after the first extrusion and cannot be cleaned in a short period of time, resulting in the inability to carry out continuous production; From the analysis results of Example 17 of the present invention and Comparative Examples 4 to 6, it can be seen that the existing low-residue and easy-to-clean compound additive is applied to the production of β-crystalline polypropylene resin. Although it is easy to clean and has no residue after the first extrusion, the β-crystalline content in the β-crystalline polypropylene resin product cannot be guaranteed, and the β-crystalline content is low; The homopolymer β-crystalline polypropylene resin, impact-resistant copolymer β-crystalline polypropylene resin and random copolymer β-crystalline polypropylene resin prepared in Examples 17 to 19 of the present invention respectively adopt the polypropylene β-crystalline compound additives which are easy to clean, have low residue and can induce high β-crystalline content prepared in Examples 14 to 16 of the present invention as raw materials. Each β-crystalline polypropylene resin has a high β-crystalline content, and a small amount of residual compound additives can be quickly taken out and cleaned from the device additive system and the extruder system in a short time, so that there is no residue and does not affect the subsequent continuous production.

[0083] In summary, the polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce a high content of β-crystals of the present invention not only adopts a compound β-crystal nucleating agent to increase the induction rate of β-crystals, but also proposes and introduces a coating release agent for the first time, and adopts a main β-crystal coating release agent + an auxiliary β-crystal coating release agent to be used in combination to play a role of coating and isolation. The composite coating release agent and the composite β-crystal nucleating agent produce a synergistic effect, so that the produced polypropylene has a high β-crystal content, and ensures that the polypropylene β-crystal nucleating agent in the additive system and the extruder system has no residue and is easy to clean, and has no influence on the production of subsequent polypropylene resin products.

[0084] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or reduced according to actual needs to meet the requirements of different situations.

Claims

1. A polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce high β-crystal content. Features The raw materials include 0.05 to 1 part of a composite β-crystal nucleating agent, 0.05 to 1 part of a composite β-crystal coating isolation agent and 0.01 to 2 parts of a composite antioxidant by weight.

2. The polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals according to claim 1, Features The raw materials include, by weight, 0.1 to 0.5 parts of a composite beta crystal nucleating agent, 0.1 to 0.2 parts of a composite beta crystal coating separator and 0.1 to 0.5 parts of a composite antioxidant.

3. The polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce high β-crystal content according to claim 1 or 2, Features The composite β-crystal nucleating agent includes 10% to 90% of a main β-crystal nucleating agent and the remainder of an auxiliary β-crystal nucleating agent by weight percentage, and is obtained by the following method: the required amount of the main β-crystal nucleating agent and the auxiliary β-crystal nucleating agent are placed in a high-speed mixer and mixed to obtain the composite β-crystal nucleating agent.

4. The polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals according to claim 3, Features The main β-crystal nucleating agent is an aromatic amide compound, and the aromatic amide compound is N,N-dicyclohexylterephthalamide.

5. The polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals according to claim 3, Features The auxiliary β-crystal nucleating agent is a carboxylate compound, and the carboxylate compound is a condensed ring supported sodium calcium pimelic acid salt.

6. The polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce high β-crystal content according to claim 1 or 2, Features The composite β-crystal coating separator comprises 1% to 99% of a main β-crystal coating separator and the remainder of an auxiliary β-crystal coating separator by weight percentage, and is obtained by the following method: the required amount of the main β-crystal coating separator and the auxiliary β-crystal coating separator are placed in a high-speed mixer and mixed to obtain the composite β-crystal coating separator.

7. The polypropylene β-crystal compound additive according to claim 6, which is easy to clean, has low residue and can induce high β-crystal content, Features The main β crystal coating isolation agent is β-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate.

8. The polypropylene β-crystal compound additive according to claim 6, which is easy to clean, has low residue and can induce high β-crystal content, Features The auxiliary β-crystal coating release agent is a polymer wax compound, and the polymer wax compound is one of vinyl polymer wax and propylene polymer wax.

9. The polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce high β-crystal content according to claim 1 or 2, Features The composite antioxidant is three or more of antioxidant 1010, antioxidant 168, antioxidant cast, antioxidant 626, antioxidant 1330, and antioxidant dgms.

10. The polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals according to claim 9, Features The composite antioxidant is a mixture of 0.02 to 0.5 parts of antioxidant 1010, 0.02 to 0.5 parts of antioxidant 168 and 0.01 to 0.1 parts of antioxidant cast in parts by weight.

11. The polypropylene β-crystal compound additive according to claim 9, which is easy to clean, has low residue and can induce high β-crystal content, Features The composite antioxidant is a mixture of 0.02 to 0.5 parts of antioxidant 1010, 0.02 to 0.5 parts of antioxidant 168, 0.02 to 0.5 parts of antioxidant 626 and 0.01 to 0.1 parts of antioxidant dgms in parts by weight.

12. The polypropylene β-crystal compound additive according to claim 9, which is easy to clean, has low residue and can induce high β-crystal content, Features The composite antioxidant is a mixture of 0.02 to 0.5 parts of antioxidant 1010, 0.02 to 0.5 parts of antioxidant 168, 0.05 to 0.5 parts of antioxidant 1330 and 0.01 to 0.1 parts of antioxidant cast in parts by weight.

13. The polypropylene β-crystal compound additive according to any one of claims 1 to 12, which is easy to clean, has low residue and can induce a high content of β-crystals. Features The method is as follows: the required amount of composite β-crystal nucleating agent, composite β-crystal coating separator and composite antioxidant are placed in a high-speed mixer and mixed to obtain a polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce high β-crystal content.

14. A method for preparing a polypropylene β-crystal compound additive that is easy to clean, has low residue and can induce a high content of β-crystals according to any one of claims 1 to 12, Features The method is as follows: the required amount of composite β-crystal nucleating agent, composite β-crystal coating separator and composite antioxidant are placed in a high-speed mixer and mixed evenly to obtain a polypropylene β-crystal compound additive which is easy to clean, has low residue and can induce high β-crystal content.

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