Modified polybutylene-1 composition, polybutylene-1 alloy material, preparation method of polybutylene-1 alloy material, honeycomb tube and application of honeycomb tube

Abstract

The invention relates to the technical field of high polymer materials, in particular to a modified polybutylene-1 composition, a polybutylene-1 alloy material, a preparation method of the polybutylene-1 alloy material, a honeycomb tube and application of the honeycomb tube. The composition comprises the following components in parts by weight: 100 parts of copolymerized polybutylene-1, 17-43 parts of homopolymerized polybutylene-1, 7-18 parts of polypropylene and 0.2-1.6 parts of auxiliaries. The polybutylene-1 alloy material is prepared from the composition, the alloy material is used for a bonding layer of a polypropylene honeycomb tube, the bonding strength and low temperature resistance of the polypropylene honeycomb tube can be remarkably improved, and the tube distribution difficulty is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a modified polybutene-1 composition, a polybutene-1 alloy material and a preparation method thereof, a honeycomb tube and applications thereof. Background Art

[0002] Honeycomb panels are widely used in the automotive industry, shipbuilding industry, gas desulfurization, construction industry, FRP and refrigeration industries. The main component of honeycomb panels is honeycomb tubes. Honeycomb tubes are mainly made of paper, plastic and aluminum materials, and have hexagonal, circular and diamond structures. Among them, polypropylene honeycomb panels based on polypropylene have the characteristics of light weight, good sound insulation, strong pressure resistance, high temperature resistance, strong heat insulation effect, water resistance and corrosion resistance. In recent years, the market share has gradually increased.

[0003] The polypropylene honeycomb tube is composed of a core layer and a bonding layer (outer layer). Among them, the bonding layer material needs to have good compatibility with the inner layer of polypropylene, a low bonding temperature and strong bonding strength, as well as good extrusion processing performance. At the same time, in order to adapt to the low-temperature use environment, the honeycomb tube bonding layer should have excellent low-temperature toughness. Polybutene-1 resin has high cohesive energy and is an excellent bonding material. It has good compatibility with polypropylene and strong interfacial bonding force. At the same time, compared with polypropylene, polybutene-1 has a lower glass transition temperature and better low-temperature toughness. However, the polybutene-1 resin has a low crystallization temperature and a slow crystallization rate, which can easily lead to application difficulties such as low extrusion efficiency and difficulty in honeycomb tube laying, which limits its application in the bonding layer of polypropylene honeycomb tubes. On the basis of maintaining the excellent low-temperature toughness and bonding performance of polybutene-1 resin, its extrusion processability is significantly improved, which has important industrial application value. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of poor low-temperature resistance, low bonding strength and great difficulty in pipe laying of polypropylene honeycomb tubes in the prior art, and to provide a modified polybutene-1 composition, a polybutene-1 alloy material and a preparation method thereof, a honeycomb tube and its application.

[0005] In view of the above problems, the inventors of the present invention discovered through research that by adding an appropriate amount of polypropylene and homopolymer polybutene-1 to copolymer polybutene-1, the resulting alloy material, when used for the bonding layer of polypropylene honeycomb tubes, can ensure the bonding strength and low temperature resistance of the honeycomb tubes while reducing the difficulty of pipe laying, thus obtaining the present invention.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a modified polybutene-1 composition, characterized in that the composition comprises: 100 parts by weight of copolymerized polybutene-1, 17-43 parts by weight of homopolymerized polybutene-1, 7-18 parts by weight of polypropylene, and 0.2-1.6 parts by weight of an auxiliary agent.

[0007] In the present invention, preferably, the polypropylene is a binary random copolymer polypropylene.

[0008] A second aspect of the present invention provides a polybutene-1 alloy material, wherein the polybutene-1 alloy material is prepared from the aforementioned composition.

[0009] The third aspect of the present invention provides a method for preparing a polybutene-1 alloy material, comprising the following steps: melt-blending and granulating the components included in the composition provided by the present invention to obtain the polybutene-1 alloy material.

[0010] A fourth aspect of the present invention provides a polybutene-1 alloy material obtained by the aforementioned preparation method.

[0011] A fifth aspect of the present invention provides a polypropylene honeycomb tube, wherein the polypropylene honeycomb tube comprises a bonding layer and a core layer.

[0012] In the present invention, preferably, the bonding layer of the polypropylene honeycomb tube comprises the polybutene-1 alloy material provided in the second aspect or the fourth aspect of the present invention.

[0013] In the present invention, preferably, the core layer of the polypropylene honeycomb tube comprises polypropylene.

[0014] A sixth aspect of the present invention provides a use of the aforementioned polypropylene honeycomb tube of the present invention in the preparation of honeycomb panels and composite panels.

[0015] Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows:

[0016] First, the components contained in the modified polybutene-1 composition provided by the present invention can make the obtained polybutene-1 alloy material have a faster crystallization rate. When the alloy material is used as the bonding layer of the polypropylene honeycomb tube, it can ensure that the polypropylene honeycomb tube has good bonding strength and low temperature resistance, and is not easy to be damaged at a temperature of -30°C. At the same time, the difficulty of laying the polypropylene honeycomb tube is greatly reduced, the machinability of the polypropylene honeycomb tube is improved, and the production cost is reduced.

[0017] Second, in the present invention, the polypropylene added to the polybutene-1 alloy material has good compatibility with the polypropylene core layer of the honeycomb tube, which helps to improve the bonding strength between the adhesive layer and the polypropylene core layer. In particular, the inventors found that when binary random copolymer polypropylene is used, the alloy material and the polypropylene core layer are better bonded.

[0018] Binary random copolymer polypropylene has a higher crystallization temperature and a faster crystallization rate, and preferentially crystallizes during extrusion molding. The inventors have found that when the composition includes binary random copolymer polypropylene, the nucleation rate of the polybutene-1 alloy material can be greatly improved. In addition, it synergizes with homopolymer polybutene-1 and additives, which is beneficial to the crystallization of the polybutene-1 alloy material; it synergizes with homopolymer polybutene-1 to enable the polybutene-1 alloy material to maintain excellent low-temperature toughness; when the polybutene-1 alloy material prepared by the composition is used as a bonding layer of a honeycomb tube, the curing speed of the polypropylene honeycomb tube can be further improved, and the difficulty of pipe laying can be reduced.

[0019] Third, the melting temperature of copolymerized polybutene-1 is extremely low. As the main component of the composition or the alloy material, it can ensure that the alloy material is easier to melt at low temperatures and improve the bonding strength of the honeycomb tube. At the same time, copolymerized polybutene-1 has extremely high low-temperature simply supported beam impact strength. When it is used as the main component of the alloy material, the alloy material can have good low-temperature toughness. When the alloy material containing this component is used in the bonding layer of the polypropylene honeycomb tube, the low-temperature resistance of the polypropylene honeycomb tube can be significantly improved.

[0020] Fourth, homopolymerized polybutene-1 has a lower melting point, a higher crystallization temperature than copolymerized polybutene-1, and a lower temperature toughness than binary random copolymerized polypropylene. Adding a proper amount can significantly reduce the amount of binary random copolymerized polypropylene added in the composition or alloy material. The alloy material containing this component is easier to soften in the thermal bonding process and has excellent low temperature toughness. Moreover, when the alloy material containing this component is used as the bonding layer of the polypropylene honeycomb tube, the bonding strength of the polypropylene honeycomb tube can be further improved. DETAILED DESCRIPTION

[0021] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0022] The first aspect of the present invention provides a modified polybutene-1 composition, wherein the composition comprises: 100 parts by weight of copolymerized polybutene-1, 17-43 parts by weight of homopolymerized polybutene-1, 7-18 parts by weight of polypropylene, and 0.2-1.6 parts by weight of an auxiliary agent.

[0023] In some preferred embodiments, the composition comprises the following components: 100 parts by weight of copolymerized polybutene-1, 18-40 parts by weight of homopolymerized polybutene-1, 8-17 parts by weight of polypropylene, and 0.5-1.2 parts by weight of an auxiliary agent.

[0024] In the above-mentioned composition provided by the present invention, a limited amount of polypropylene and homopolymer polybutene-1 cooperate with each other, so that the polybutene-1 alloy material containing the composition has a faster nucleation speed and is easier to soften at low temperatures. When the alloy material is used for the bonding layer of the polypropylene honeycomb tube, the bonding strength and low temperature resistance of the polypropylene honeycomb tube can be significantly improved, and the difficulty of pipe laying can be greatly reduced.

[0025] In some embodiments, the homopolymerized polybutene-1 has a melt index of 5-15 g / 10 min, preferably 8-12 g / 10 min, at 190° C. and a load of 2.16 kg. The homopolymerized polybutene-1 can be commercially available, for example, from the Zhenhai Refining and Chemical Company of China Petrochemical Corporation.

[0026] In the present invention, when the melt index of homopolymerized polybutene-1 satisfies the above preferred range, the obtained polybutene-1 alloy material can be more easily softened at low temperatures (eg, 120-130° C.) and can maintain good low-temperature toughness.

[0027] In some preferred embodiments, the copolymerized polybutene-1 is a random copolymerized polybutene-1.

[0028] In some embodiments, the random copolymer polybutene-1 has a melt index of 5-15 g / 10 min at 190° C. and a load of 2.16 kg.

[0029] In some preferred embodiments, the second comonomer of the random copolymer polybutene-1 is ethylene, and the content of the ethylene structural unit is 1.5-10 mol%, preferably 2-8 mol%, based on the total weight of the random copolymer polybutene-1. The ethylene structural unit refers to the part of the ethylene monomer that is bonded to the macromolecular chain of the random copolymer polybutene-1 through the carbon-carbon double bond in ethylene through addition polymerization. The random copolymer polybutene-1 can be commercially available, for example, from Zhenhai Refining and Chemical Company of China Petrochemical Corporation.

[0030] In the present invention, when the melt index and the content of ethylene structural units of the random copolymer polybutene-1 meet the above ranges, the low-temperature toughness of the polybutene-1 alloy material prepared from the composition can be guaranteed, and the alloy material is more easily softened at low temperatures (e.g., 120-130°C). When the polybutene-1 alloy material is used for the bonding layer of a polypropylene honeycomb tube, the bonding strength of the polypropylene honeycomb tube is significantly improved.

[0031] In some preferred embodiments, the polypropylene is a binary random copolymer polypropylene.

[0032] In some preferred embodiments, the binary random copolymer polypropylene has a melt index of 10-35 g / 10 min, preferably 20-28 g / 10 min, at 230° C. and a load of 2.16 kg.

[0033] In some preferred embodiments, the second comonomer of the binary random copolymer polypropylene is ethylene, and the content of the ethylene structural unit is 4-12 mol%, preferably 6-10 mol%, based on the total weight of the binary random copolymer polypropylene. The ethylene structural unit refers to the part of the ethylene monomer that is bonded to the macromolecular chain of the binary random copolymer polypropylene through the carbon-carbon double bond in ethylene through addition polymerization. The binary random copolymer polypropylene can be commercially available, for example, from Zhenhai Refining and Chemical Company of China Petrochemical Corporation.

[0034] In the present invention, when the melt index and the content of the ethylene structural unit of the binary random copolymer polypropylene meet the above ranges, the low-temperature toughness of the polybutene-1 alloy material prepared from the composition can be guaranteed, and the alloy material is more easily softened at low temperatures (e.g., 120-130° C.). When the polybutene-1 alloy material is used for the bonding layer of a polypropylene honeycomb tube, the difficulty of laying the polypropylene honeycomb tube is greatly reduced.

[0035] In some embodiments, the auxiliary agent includes an antioxidant, a nucleating agent, a dispersant, and an acid scavenger.

[0036] In some preferred embodiments, the weight ratio of antioxidant, nucleating agent, dispersant and acid scavenger is 1:(0.2-2.5):(0.2-2.5):(0.1-1.5); preferably 1:(0.5-2):(0.5-2):(0.2-1).

[0037] In the present invention, the antioxidant is an antioxidant commonly used in the art. In some embodiments of the present invention, preferably, the antioxidant is a phosphite antioxidant and / or a hindered phenol antioxidant, more preferably one or more of tris(2,4-di-tert-butyl)phenyl phosphite (Antioxidant 168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Antioxidant 100), and n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Antioxidant 1076).

[0038] In the present invention, the nucleating agent is a nucleating agent commonly used in the art. In some embodiments of the present invention, preferably, the nucleating agent is one or more of a carboxylate nucleating agent, a phosphate nucleating agent and an isosorbide nucleating agent.

[0039] In the present invention, the dispersant is a commonly used dispersant in the art. In some embodiments of the present invention, preferably, the dispersant is one or more of stearic acid amide, fatty acid derivatives and oleic acid amide, more preferably stearic acid amide, and further preferably ethylene bisstearamide (EBS).

[0040] In the present invention, the acid scavenger is a commonly used acid scavenger in the art. In some embodiments of the present invention, preferably, the acid scavenger is one or more of hydrotalcite, calcium stearate and zinc stearate.

[0041] A second aspect of the present invention provides a polybutene-1 alloy material, wherein the polybutene-1 alloy material is prepared from the aforementioned composition.

[0042] In the present invention, differential scanning calorimetry (DSC) is used to test the thermal properties of the polybutene-1 alloy material at a heating and cooling rate of 10°C / min. If the material has two melting temperatures, the higher melting temperature is recorded as the first melting temperature, and the lower melting temperature is recorded as the second melting temperature; the percentage of the higher melting peak integrated enthalpy value to the total integrated enthalpy values ​​of the two melting peaks is recorded as the first melting peak melting enthalpy ratio; the higher crystallization temperature is recorded as the first crystallization temperature, and the lower crystallization temperature is recorded as the second crystallization temperature.

[0043] In the present invention, preferably, the polybutene-1 alloy material, when measured by differential scanning calorimetry, satisfies the conditions of having double melting peaks and double crystallization peaks at a heating and cooling rate of 10°C / min; wherein the first melting temperature is below 160°C, the melting enthalpy of the first melting peak accounts for less than 18%, the second melting temperature is below 117°C, the first crystallization temperature is above 115°C, the second crystallization temperature is above 70°C, and the simply supported beam impact strength at -30°C is 2 kJ / m 2 above.

[0044] In the present invention, the simply supported beam impact strength of the polybutene-1 alloy material at -30°C is measured according to GB / T1043.1-2008. When the thermal property parameters and simply supported beam impact strength of the polybutene-1 alloy material meet the above ranges, the alloy material has a faster nucleation rate and is easier to soften at low temperatures (e.g., 120-130°C); when the alloy material is used as a bonding layer, the bonding strength of the prepared polypropylene honeycomb tube is improved, the low temperature resistance is good, and the difficulty of pipe laying is greatly reduced.

[0045] The third aspect of the present invention provides a method for preparing a polybutene-1 alloy material, the method comprising the following steps: melt-blending and granulating the components of the composition provided by the present invention to obtain the polybutene-1 alloy material.

[0046] In a specific embodiment provided by the present invention, the preparation method may include: adding the components of the composition provided by the present invention into a twin-screw extruder, blending and granulating, and stranding and pelletizing to prepare polybutene-1 alloy pellets.

[0047] In the present invention, there is no particular limitation on the blending time, blending temperature and extrusion temperature in the above steps, and they can be carried out according to conventional conditions in the art.

[0048] In some specific embodiments of the present invention, preferably, the blending time of the blending granulation conditions is 5-30 min, preferably 6-12 min.

[0049] In some specific embodiments of the present invention, preferably, the blending temperature is 200-250°C, such as 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, and any value in the range consisting of any two of the above values.

[0050] In some specific embodiments of the present invention, preferably, the extrusion temperature is 180-230°C, such as 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, and any value in the range consisting of any two of the above values.

[0051] In some specific embodiments of the present invention, the components of the composition include: 100 parts by weight of copolymerized polybutene-1, 17-43 parts by weight of homopolymerized polybutene-1, 7-18 parts by weight of polypropylene, and 0.2-1.6 parts by weight of an auxiliary agent. When the components are within the above ranges, the obtained polybutene-1 alloy material has good compatibility with polypropylene and is easy to melt at low temperatures (e.g., 120-130° C.).

[0052] According to a preferred embodiment of the present invention, the components of the composition include: 100 parts by weight of copolymerized polybutene-1, 18-40 parts by weight of homopolymerized polybutene-1, 8-17 parts by weight of polypropylene, and 0.5-1.2 parts by weight of an auxiliary agent. When the components are within the above range, the obtained polybutene-1 alloy material has better compatibility with polypropylene, is easier to melt at low temperatures (e.g., 120-130° C.), and when the alloy material is used as a bonding layer of a polypropylene honeycomb tube, the polypropylene honeycomb tube has better performance such as pipe laying difficulty, bonding strength, and low temperature resistance.

[0053] A fourth aspect of the present invention provides a polybutene-1 alloy material obtained by the aforementioned preparation method.

[0054] In the present invention, preferably, the polybutene-1 alloy material, when measured by differential scanning calorimetry, satisfies the conditions of having double melting peaks and double crystallization peaks at a heating and cooling rate of 10°C / min; wherein the first melting temperature is below 160°C, the melting enthalpy of the first melting peak accounts for less than 18%, the second melting temperature is below 117°C, the first crystallization temperature is above 115°C, the second crystallization temperature is above 70°C, and the simply supported beam impact strength at -30°C is 2 kJ / m 2 above.

[0055] In the present invention, when the first melting temperature, the first melting peak melting enthalpy ratio, the second melting temperature, the first crystallization temperature, the second crystallization temperature and the simply supported beam impact strength at -30°C of the polybutene-1 alloy material are within the above ranges, the alloy material is used as a bonding layer, and the bonding strength of the prepared polypropylene honeycomb tube is improved, the low temperature resistance is good, and the difficulty of pipe laying is greatly reduced.

[0056] A fifth aspect of the present invention provides a polypropylene honeycomb tube, wherein the polypropylene honeycomb tube comprises a bonding layer and a core layer.

[0057] In the present invention, preferably, the bonding layer of the polypropylene honeycomb tube comprises the polybutene-1 alloy material provided in the second aspect or the fourth aspect of the present invention.

[0058] In the present invention, preferably, the core layer of the polypropylene honeycomb tube comprises polypropylene.

[0059] A sixth aspect of the present invention provides an application of the polypropylene honeycomb tube of the present invention in the preparation of honeycomb panels and composite panels.

[0060] The present invention will be described in detail below through examples.

[0061] In the following examples and comparative examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are conventional products that can be obtained through commercial channels. The details are as follows:

[0062] (I) Main raw materials:

[0063] (1) Random copolymerization of polybutene-1:

[0064] Brand PBR-F08, China Petrochemical Corporation Zhenhai Refining and Chemical Company, melting point 105°C, melt index 8g / 10min (190°C / 2.16kg), crystallization temperature 52°C, ethylene structural unit content 2mol%;

[0065] Brand PBR-F15, China Petrochemical Corporation Zhenhai Refining and Chemical Company, melting point 82°C, melt index 15g / 10min (190°C / 2.16kg), crystallization temperature 32°C, ethylene structural unit content 8mol%;

[0066] Brand PBR-F12, China Petrochemical Corporation Zhenhai Refining and Chemical Company, melting point 119°C, melt index 12g / 10min (190°C / 2.16kg), crystallization temperature 57°C, ethylene structural unit content 1mol%;

[0067] (2) Homopolymer polybutene-1: brand PBH-F10, produced by Zhenhai Refining and Chemical Company of China Petrochemical Corporation, melting point 129°C, melt index 10g / 10min (190°C / 2.16kg), crystallization temperature 82°C;

[0068] (3) Binary random copolymer polypropylene: grade M26ETN, produced by Zhenhai Refining and Chemical Company of China Petrochemical Corporation, melting point 155°C, melt index 26g / 10min (230°C / 2.16kg), crystallization temperature 125°C, content of ethylene structural unit 7mol%;

[0069] (4) Ternary random copolymer polypropylene: brand F4908, Maoming Branch of Sinopec, melting point 135°C, melt index 8g / 10min (230°C / 2.16kg), crystallization temperature 107°C; content of ethylene structural unit 10mol%, content of butene structural unit 1mol%;

[0070] (5) Homopolymer polypropylene: brand Y26, produced by Zhenhai Refining and Chemical Company of China Petrochemical Corporation, melting point 165°C, melt index 26 g / 10 min (230°C / 2.16 kg), crystallization temperature 137°C.

[0071] (II) Main equipment:

[0072] Twin-screw extruder: ZSM MAXX, Leistrite, Germany;

[0073] Single screw double-layer tube extruder: Model 65, Qingdao Yasente Machinery Co., Ltd.

[0074] Industrial oven: WD704, Wujiang Wanda Electric Heating Equipment;

[0075] Mechanical properties: 5567 universal testing machine, Instron, USA;

[0076] Thermodynamic testing equipment: DSC, TA Company, USA.

[0077] (III) Test methods:

[0078] (1) Melt index: The melt index of copolymer polybutene-1 and homopolybutene-1 was measured according to GB / T 37199.2-2018, and the test conditions were 190°C and a load of 2.16 kg. The melt index of polypropylene was measured according to GB / T 3682.1-2-2018, and the test conditions were 230°C and a load of 2.16 kg.

[0079] (2) Thermal property test of polybutene-1 alloy material: DSC was used to measure the melting and crystallization characteristics of the alloy materials obtained in each embodiment and comparative example. The heating and cooling rates were 10°C / min and -10°C / min, respectively. The upper limit of heating was 220°C, and the lower limit of cooling was -20°C. The first heating eliminated the thermal history. The melting characteristics were taken from the second heating data, and the crystallization characteristics were taken from the first cooling data.

[0080] (3) Charpy notched impact strength of polybutene-1 alloy material at -30°C: The Charpy notched impact strength of the alloy material at -30°C was measured according to GB / T 1043.1-2008. The processing method of the test standard specimen is as follows: a 4 mm thick plate is prepared by pressing at 180°C, 5 MPa and a cooling rate of 20°C / min, the plate is processed into a 4 mm × 10 mm × 80 mm specimen by a punching machine, and the specimen is processed by a machine to obtain a standard specimen with an A-notch.

[0081] (4) Bonding strength test of polypropylene honeycomb tube: The honeycomb panel after thermal bonding was cut into samples with a thickness of 18 mm, a length of 200 mm, and a width of 50 mm. A tensile test was performed using a universal testing machine at a tensile rate of 10 mm / min to obtain the bonding strength of the polypropylene honeycomb tube.

[0082] (5) Adhesion rate of polypropylene honeycomb tubes: at an extrusion speed of 280 m / min, the honeycomb tubes were placed in a 25°C water tank for 30 s after exiting the die, cut into short tubes of 400 mm in length, and immediately arranged in sequence. After cooling at room temperature for 30 min, the number of adhered honeycomb tubes was manually counted, and the percentage of adhered honeycomb tubes in the total honeycomb tubes was calculated.

[0083] (6) Low-temperature drop breakage rate of polypropylene honeycomb tubes: After thermal bonding, the polypropylene honeycomb tubes were cooled and cut to prepare samples with a thickness of 18 mm, a length of 200 mm, and a width of 50 mm. The samples were kept at a constant temperature of -30°C in a cold storage for 24 hours. The honeycomb panel samples were allowed to fall freely at a height of 3 meters from the ground, and the percentage of broken samples in the total samples was calculated.

[0084] The results of the thermal property test, the simple supported beam notched impact strength test at -30°C, the bonding strength test, the pipe adhesion rate test and the low temperature drop breakage rate are shown in Tables 2 and 3.

[0085] Example 1

[0086] 1) The formula of alloy materials includes:

[0087] Random copolymer polybutene-1, PBR-F08, 100 parts by weight;

[0088] Homopolymer polybutene-1, PBH-F10, 18 parts by weight;

[0089] Binary random copolymer polypropylene, M26ETN, 17 parts by weight;

[0090] Additives: 0.2 parts by weight of antioxidant 1010 / 168, nucleating agent Hyperform HPN-68L, EBS and calcium stearate in total, wherein the weight ratio of antioxidant 1010 / 168, Hyperform HPN-68L, EBS and calcium stearate is 1:2:2:0.2.

[0091] 2) The specific preparation method is as follows:

[0092] The above resin and additives were added into a twin-screw extruder for blending and granulation. The blending time was 10 min, the blending temperature was 220° C., the extrusion temperature was 190-220° C., the die temperature was 200° C., and the strands were cut into pellets to prepare a polybutene-1 alloy material.

[0093] The thermal properties and the notched impact strength of the obtained polybutene-1 alloy material at -30°C are shown in Table 2.

[0094] Example 2-3

[0095] The polybutene-1 alloy material was prepared in the same manner as in Example 1, except that the formula of the alloy material was different, as shown in Table 1. The thermal properties and the simple supported beam notched impact strength at -30°C of the obtained polybutene-1 alloy material are shown in Table 2.

[0096] Comparative Examples 1-10

[0097] The polybutene-1 alloy material was prepared in the same manner as in Example 1, except that the formula of the alloy material was different, as shown in Table 1; the thermal properties and the simply supported beam notched impact strength at -30°C of the obtained polybutene-1 alloy material were shown in Table 2.

[0098] Table 1

[0099]

[0100]

[0101] Table 2

[0102]

[0103]

[0104] Application Examples

[0105] Polypropylene (grade: M10RG, melt index: 10g / 10min (230℃ / 2.16kg, Zhenhai Refining and Chemical Company of China Petrochemical Corporation), and the polybutene-1 alloy materials of each embodiment and comparative example are respectively added into a single-screw double-layer extruder for extrusion molding, the inner layer of the extruder uses polypropylene, and the outer layer uses the polybutene-1 alloy pellets prepared above, the inner layer extrusion temperature is 220℃, the outer layer extrusion temperature is 200℃, the mass ratio of the inner and outer layer raw materials is 9:1, the inner diameter is 6mm, and the outer diameter is 7mm;

[0106] After the polypropylene honeycomb tube leaves the die, it stays in a 25℃ water tank for 30 seconds, and is cut into 400mm lengths. The honeycomb tubes are arranged in sequence and wait for thermal bonding;

[0107] The neatly arranged polypropylene honeycomb tubes were placed in an oven with a bonding time of 30 minutes and a bonding temperature of 125°C.

[0108] The bonding strength, pipe adhesion rate and low-temperature drop breakage rate of the polypropylene honeycomb tube after thermal bonding were tested, and the results are shown in Table 3.

[0109] Table 3

[0110]

[0111]

[0112] It can be seen from the results in Table 2 and Table 3 that: by using a specific amount of random copolymer polybutene-1, homopolymer polybutene-1, binary random copolymer polypropylene and additives in combination, the polybutene-1 alloy material comprising the composition has a higher crystallization temperature, a lower melting point, and good low-temperature toughness; the polypropylene honeycomb tube comprising the above polybutene-1 alloy material has high bonding strength, high low-temperature resistance, and low pipe laying difficulty.

[0113] Specifically, compared with the comparative example, there is no adhesion between the polypropylene honeycomb tubes made of the polybutene-1 alloy material of the embodiment as the bonding layer; the honeycomb panel after thermal bonding is cut into samples with a thickness of 18 mm, a length of 200 mm, and a width of 50 mm, and a tensile test is performed using a universal testing machine at a tensile rate of 10 mm / min, and the bonding strength of the polypropylene honeycomb tube is obtained to be above 8N; the bonded honeycomb tube is kept at a constant temperature in a -30°C low-temperature cold storage for 24 hours, and the honeycomb panel sample is freely dropped 3 meters above the ground, and the low-temperature drop breakage rate is less than 5%.

[0114] Comparative Examples 1 and 2 do not add the homopolymer polybutene-1 or binary random copolymer polypropylene defined in the present invention. When the obtained alloy materials are used as the bonding layer of the polypropylene honeycomb tube, the adhesion rate of the polypropylene honeycomb tube is high and the tube cannot be laid.

[0115] In Comparative Example 3, excessive amounts of homopolymerized polybutene-1 and binary random copolymerized polypropylene are added, and the content of high melting point components in the obtained polybutene-1 alloy material is too high and the low-temperature toughness is poor. Although the adhesion rate of the polypropylene honeycomb tube is low when the alloy material is used as the bonding layer of the polypropylene honeycomb tube, it is not easy to soften during the hot bonding process, the bonding strength is too low, and the low-temperature drop breakage rate is high, and the low-temperature resistance is poor.

[0116] The content of homopolymer polybutene-1 and binary random copolymer polypropylene in Comparative Example 4 is too low, and the obtained polybutene-1 alloy material has poor crystallization ability and slow nucleation rate. The adhesion rate of the polypropylene honeycomb tube using the alloy material as the bonding layer is high, and the pipe laying is difficult.

[0117] Comparative Examples 5-7 only add one resin. Comparative Example 5 only adds homopolymerized polybutene-1, and the content of low melting point components of the alloy material obtained is very small, and the bonding strength of the polypropylene honeycomb tube is low; Comparative Example 6 only adds random copolymerized polybutene-1, and the crystallization ability of the alloy material obtained is poor, and the pipe laying of the polypropylene honeycomb tube is extremely difficult; Comparative Example 7 only adds binary random polypropylene, and the content of low melting point components of the alloy material obtained is very small, resulting in insufficient bonding strength of the polypropylene honeycomb tube and poor low temperature resistance.

[0118] In comparative example 8, random copolymer polybutene-1 with an ethylene structural unit content of only 1% is added, which cannot improve the bonding strength and low temperature resistance of the alloy polypropylene honeycomb tube obtained. This is because the second melting temperature of the polybutene-1 alloy material containing this component is too high, which makes the polypropylene honeycomb tube difficult to soften during thermal bonding.

[0119] Comparative Example 9 uses ternary random copolymer polypropylene instead of binary random copolymer polypropylene. The resulting polypropylene-1 alloy material has a low crystallization temperature. When the alloy material is used as a bonding layer, the adhesion rate of the polypropylene honeycomb tube is high, the tube cannot be laid, and the processability is poor.

[0120] Comparative Example 10 uses homopolymer polypropylene instead of binary random copolymer polypropylene. The resulting polybutene-1 alloy material has poor low-temperature toughness, too high a first melting peak melting point, and too high a proportion of the first melting peak melting enthalpy. When this alloy material is used as a bonding layer, the bonding strength and low-temperature resistance of the polypropylene honeycomb tube cannot be improved.

[0121] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various specific technical features in any suitable manner. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations. However, these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A modified polybutene-1 composition, characterized in that The composition comprises: 100 parts by weight of copolymerized polybutene-1, 17-43 parts by weight of homopolymerized polybutene-1, 7-18 parts by weight of polypropylene, and 0.2-1.6 parts by weight of an auxiliary agent.

2. The composition according to claim 1, wherein The composition comprises: 100 parts by weight of copolymerized polybutene-1, 18-40 parts by weight of homopolymerized polybutene-1, 8-17 parts by weight of polypropylene, and 0.5-1.2 parts by weight of an auxiliary agent.

3. The composition according to claim 1 or 2, wherein The melt index of the homopolymer polybutene-1 at 190° C. and a load of 2.16 kg is 5-15 g / 10 min, preferably 8-12 g / 10 min; Preferably, the copolymerized polybutene-1 is a random copolymerized polybutene-1; And / or, the random copolymer polybutene-1 has a melt index of 5-15 g / 10 min at 190° C. and a load of 2.16 kg; And / or, the second comonomer of the random copolymerized polybutene-1 is ethylene, and the content of the ethylene structural unit is 1.5-10 mol%, preferably 2-8 mol%, based on the total weight of the random copolymerized polybutene-1.

4. The composition according to any one of claims 1 to 3, wherein The polypropylene is a binary random copolymer polypropylene; Preferably, the binary random copolymer polypropylene has a melt index of 10-35 g / 10 min at 230° C. and a load of 2.16 kg, preferably 20-28 g / 10 min; And / or, the second comonomer of the binary random copolymer polypropylene is ethylene, and the content of the ethylene structural unit is 4-12 mol%, preferably 6-10 mol%, based on the total weight of the binary random copolymer polypropylene.

5. The composition according to any one of claims 1 to 4, wherein The auxiliary agents include antioxidants, nucleating agents, dispersants and acid scavengers; Preferably, the weight ratio of antioxidant, nucleating agent, dispersant and acid scavenger is 1:(0.2-2.5):(0.2-2.5):(0.1-1.5); preferably 1:(0.5-2):(0.5-2):(0.2-1); Preferably, the antioxidant is a phosphite antioxidant and / or a hindered phenol antioxidant, preferably one or more of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; Preferably, the nucleating agent is one or more of a carboxylate nucleating agent, a phosphate nucleating agent and an isosorbide nucleating agent; Preferably, the dispersant is one or more of stearic acid amide, fatty acid derivatives and oleic acid amide, preferably stearic acid amide; Preferably, the acid scavenger is one or more of hydrotalcite, calcium stearate and zinc stearate.

6. A polybutene-1 alloy material, characterized in that: The polybutene-1 alloy material is made from the composition described in any one of claims 1 to 5; Preferably, when the polybutene-1 alloy material is measured by differential scanning calorimetry, it has double melting peaks and double crystallization peaks at a heating and cooling rate of 10°C / min; wherein the first melting temperature is below 160°C, the melting enthalpy of the first melting peak accounts for less than 18%, the second melting temperature is below 117°C, the first crystallization temperature is above 115°C, the second crystallization temperature is above 70°C, and the simply supported beam impact strength at -30°C is 2 kJ / m 2 above.

7. A method for preparing a polybutene-1 alloy material, characterized in that: The method comprises the following steps: melt-blending and granulating the components of the composition according to any one of claims 1 to 5 to obtain a polybutene-1 alloy material; Preferably, the conditions for melt blending and granulation include: blending time of 5-30 min; blending temperature of 200-250°C; and extrusion temperature of 180-230°C.

8. A polybutene-1 alloy material obtained by the preparation method according to claim 7; Preferably, the polybutene-1 alloy material has a double melting peak and a double crystallization peak at a heating and cooling rate of 10°C / min when measured by differential scanning calorimetry; wherein, The first melting temperature is below 160°C, the first melting peak melting enthalpy accounts for less than 18%, the second melting temperature is below 117°C, the first crystallization temperature is above 115°C, the second crystallization temperature is above 70°C, and the simply supported beam impact strength at -30°C is 2kJ / m 2 above.

9. A polypropylene honeycomb tube, characterized in that: The polypropylene honeycomb tube comprises a bonding layer and a core layer; Preferably, the bonding layer of the polypropylene honeycomb tube comprises the polybutene-1 alloy material according to claim 6 or claim 8; Preferably, the core layer of the polypropylene honeycomb tube comprises polypropylene.

10. Use of the polypropylene honeycomb tube according to claim 9 in the preparation of honeycomb panels and composite panels.

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