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

Abstract

The invention relates to the technical field of high polymer materials, and discloses a modified polybutylene-1 / polypropylene composition, a polybutylene-1 / polypropylene alloy material, a preparation method of the polybutylene-1 / polypropylene alloy material, a honeycomb tube and application of the honeycomb tube. The modified polybutylene-1 / polypropylene composition is prepared from the following components in parts by weight: 100 parts of copolymerized polybutylene-1, 20 to 85 parts of polypropylene and 0.2 to 1.4 parts of auxiliaries. The polybutylene-1 / polypropylene alloy material is prepared from the modified polybutylene-1 / polypropylene composition, and when the polybutylene-1 / polypropylene alloy material is used as a polypropylene honeycomb tube bonding layer, the pipe distribution difficulty of the polypropylene honeycomb tube can be reduced, processing is easy, and the bonding strength of the polypropylene honeycomb tube is remarkably improved.

Description

Technical Field

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

[0002] Polypropylene has excellent properties such as good processability, heat resistance, recyclability, and strong mechanical strength. It is the second largest general-purpose plastic in the world. Its honeycomb panels have the advantages of high strength-to-weight ratio, uniform force, strong pressure resistance, good thermal insulation performance, good shock resistance, light weight, sound insulation, non-water absorption, and stable performance in a wide temperature range. As an environmentally friendly panel, polypropylene honeycomb panels are widely used in high value-added application scenarios such as product packaging, automotive interiors, and automotive insulation boxes.

[0003] Polypropylene honeycomb panels are generally made of honeycomb tubes formed by polypropylene extrusion, through cooling, cutting, pipe laying, thermal bonding and other steps. Among them, the polypropylene honeycomb tube is composed of a core layer and a bonding layer (outer layer). The bonding layer is generally composed of polymer materials. In order to improve the bonding strength, the bonding layer material needs to have good compatibility with the inner layer of polypropylene; in the extrusion molding process, the bonding layer material needs to solidify quickly to ensure the efficiency of honeycomb tube molding and pipe laying; in the thermal bonding process, in order to improve the bonding strength of the honeycomb tube, the bonding layer material needs to have a sufficient amount of low-melting point components.

[0004] However, polybutene-1 resin has a low crystallization temperature and a slow crystallization rate. When polybutene-1 resin is used to bond with polypropylene honeycomb tubes, it is easy to cause application difficulties such as low extrusion efficiency of honeycomb tubes and great difficulty in laying honeycomb tubes. Therefore, in order to overcome the molding difficulties of existing polybutene-1 resins, it is necessary to develop a new type of polybutene-1 modified resin. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems in the prior art of using polybutene-1 resin as a bonding layer of polypropylene honeycomb tubes, such as difficulty in laying polypropylene honeycomb tubes and low bonding strength, and to provide a modified polybutene-1 / polypropylene composition, a polybutene-1 / polypropylene alloy material and a preparation method thereof, a honeycomb tube and application thereof.

[0006] In view of the above problems, the inventors of the present invention discovered that mixing an appropriate amount of polypropylene and copolymerized polybutene-1 and using them as the bonding layer of the polypropylene honeycomb tube can maintain the excellent compatibility between the bonding layer of the polypropylene honeycomb tube and the core layer polypropylene, reduce the difficulty of laying the polypropylene honeycomb tube, facilitate processing, and provide sufficient bonding strength, thus obtaining the present invention.

[0007] In order to achieve the above object, the first aspect of the present invention provides a modified polybutene-1 / polypropylene composition, wherein the composition comprises: 100 parts by weight of copolymerized polybutene-1, 20-85 parts by weight of polypropylene, and 0.2-1.4 parts by weight of an auxiliary agent.

[0008] In the present invention, preferably, the polypropylene is a terpolymer random copolymer polypropylene.

[0009] A second aspect of the present invention provides a polybutene-1 / polypropylene alloy material, wherein the polybutene-1 / polypropylene alloy material is prepared from the aforementioned composition.

[0010] The third aspect of the present invention provides a method for preparing a polybutene-1 / polypropylene alloy material, comprising the following steps: blending the components of the composition provided by the present invention to obtain a mixed material, and extruding and granulating the mixed material.

[0011] The fourth aspect of the present invention provides a polybutene-1 / polypropylene alloy material obtained by the aforementioned preparation method.

[0012] 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.

[0013] In the present invention, preferably, the bonding layer of the polypropylene honeycomb tube comprises the polybutene-1 / polypropylene alloy material provided in the second aspect or the fourth aspect of the present invention.

[0014] In the present invention, preferably, the core layer of the polypropylene honeycomb tube comprises polypropylene.

[0015] A sixth aspect of the present invention provides the use of the aforementioned polypropylene honeycomb tube in the preparation of honeycomb panels and composite panels.

[0016] Through the above technical solution, the beneficial technical effects achieved by the present invention are as follows:

[0017] First, the modified polybutene-1 / polypropylene composition provided by the present invention can make the obtained polybutene-1 / polypropylene alloy material have a high crystallization temperature and a fast crystallization rate by virtue of the components contained therein, and the polypropylene honeycomb tube comprising the material has low pipe laying difficulty and is easier to process; at the same time, because the alloy material has an appropriate amount of components with a low melting point, it can be ensured that it is easy to soften at low temperatures (e.g., 120-130°C), and the obtained polypropylene honeycomb tube has high bonding strength. The polypropylene honeycomb tube comprising the alloy material has a balance between low pipe laying difficulty and high bonding strength.

[0018] Second, polypropylene has a higher crystallization temperature and preferentially crystallizes during extrusion molding, which can increase the initial crystallization temperature of polybutene-1 and promote the nucleation of polybutene-1. In particular, the inventors found that when ternary random copolymer polypropylene is added to the alloy material, the adhesive layer of the obtained polypropylene honeycomb tube can solidify faster and form a synergistic effect with other additives, thereby further improving the curing rate of the adhesive layer of the polypropylene honeycomb tube, reducing the difficulty of laying the polypropylene honeycomb tube, and improving the processing efficiency.

[0019] Third, when a small amount of polypropylene is used as the bonding layer of the polypropylene honeycomb tube, the bonding strength between the bonding layer and the polypropylene core layer can be further improved.

[0020] Fourth, the ternary random copolymer polypropylene has an appropriate melting point, and the appropriate amount of addition can still meet the application requirements of low-temperature bonding molding. Therefore, the obtained polybutene-1 / polypropylene alloy material has a balance of high bonding strength and efficient molding processing performance. 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] In the present invention, differential scanning calorimetry is used to test the thermal properties of the polybutene-1 / polypropylene 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.

[0023] The first aspect of the present invention provides a polybutene-1 / polypropylene composition, wherein the composition comprises: 100 parts by weight of copolymerized polybutene-1, 20-85 parts by weight of polypropylene, and 0.2-1.4 parts by weight of an auxiliary agent.

[0024] In the present invention, the weight proportion of the polypropylene can be 20, 23, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, and any value in the range consisting of any two of the values, preferably 25-80 weight proportions. At this weight proportion, the nucleation rate of the copolymerized polybutene-1 can be further accelerated and the polybutene-1 / polypropylene alloy material can be kept easy to soften under low temperature processing conditions (e.g., 120-130°C).

[0025] In the present invention, the weight portion of the auxiliary agent can be 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4 and any value in the range consisting of any two values ​​therein, preferably 0.4-1 weight portion. At this weight portion, the nucleation rate of the copolymerized polybutene-1 can be further accelerated.

[0026] According to a preferred embodiment of the present invention, the composition comprises the following components: 100 parts by weight of copolymerized polybutene-1, 25-80 parts by weight of polypropylene, and 0.4-1 parts by weight of an auxiliary agent. When the components are within the above ranges, the polybutene-1 / polypropylene alloy material comprising the composition has a faster solidification rate and can maintain the property of being easy to soften at low temperatures.

[0027] In the present invention, in order to meet the application requirements of low-temperature bonding of polypropylene honeycomb tubes, preferably, the copolymerized polybutene-1 is a random copolymerized polybutene-1.

[0028] In the present invention, preferably, the second comonomer of the random copolymer polybutene-1 is ethylene, and the content of the ethylene structural unit is 1-10 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.

[0029] In the present invention, preferably, the random copolymerized polybutene-1 has a melt index of 8-15 g / 10 min at 230° C. and a load of 2.16 kg.

[0030] In the present invention, preferably, the melting point of the random copolymerized polybutene-1 is 80-110°C.

[0031] In the present invention, preferably, the polypropylene is a terpolymer random copolymer polypropylene.

[0032] In the present invention, preferably, the second comonomer of the terpolymerized 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 terpolymerized polypropylene. The ethylene structural unit refers to the part of the ethylene monomer that is bonded to the macromolecular chain of the terpolymerized polypropylene through the carbon-carbon double bond in ethylene through addition polymerization.

[0033] In the present invention, preferably, the third comonomer of the terpolymer random copolymer polypropylene is butene.

[0034] In the present invention, preferably, the butene is 1-butene.

[0035] In the present invention, preferably, based on the total weight of the ternary random copolymer polypropylene, the content of the butene structural unit is 0.5-10 mol%, preferably 1-6 mol%. Wherein, the butene structural unit refers to the part of the butene monomer that is bonded to the macromolecular chain of the ternary random copolymer polypropylene through the carbon-carbon double bond in the butene through the addition polymerization reaction. The ternary random copolymer polypropylene can be commercially available, for example, purchased from Maoming Branch of Sinopec Corporation and The Polyolefin Company (Singapore) Pte Ltd.

[0036] In the present invention, preferably, the terpolymer random copolymer polypropylene has a melt index of 8-35 g / 10 min at 230° C. and a load of 2.16 kg.

[0037] In the present invention, preferably, the melting point of the terpolymer random copolymer polypropylene is 125-140°C, more preferably 127-135°C.

[0038] The inventors of the present invention have found that when the melting point of the added polypropylene is high, the crystallization temperature of the obtained polybutene-1 / polypropylene alloy material is increased, the crystallization rate is fast, the honeycomb tube after extrusion molding will not stick together, and the difficulty of pipe laying is greatly reduced. However, if the polypropylene with too high melting point is added, such as homopolymer polypropylene or binary random copolymer polypropylene, the bonding strength is greatly reduced. In addition, in the present invention, if the amount of ternary random copolymer polypropylene is too large, the proportion of the high melting point component in the obtained alloy material is too large, which will also affect the bonding strength of the obtained honeycomb tube.

[0039] In the present invention, the melt index, melting point and content of structural units of the ternary random copolymer polypropylene meet the above ranges. An appropriate amount of addition can significantly increase the crystallization temperature of the polybutene-1 / polypropylene alloy material without significantly increasing the proportion of high melting point components in the polybutene-1 / polypropylene alloy material, and has the technical effect of increasing the solidification rate of the alloy material while maintaining easy softening during thermal bonding.

[0040] In the present invention, preferably, the auxiliary agent includes an antioxidant, a nucleating agent, a dispersant and an acid scavenger.

[0041] In the present invention, preferably, the weight ratio of the antioxidant, nucleating agent, dispersant and acid scavenger is 1:(0.5-2.5):(0.2-2.5):(0.1-2); preferably 1:(0.5-2):(0.5-2):(0.2-1).

[0042] In the present invention, the antioxidant is a common antioxidant in the art. According to a preferred embodiment of the present invention, 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 (Antioxidant 168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Antioxidant 100), and n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Antioxidant 1076).

[0043] In the present invention, the nucleating agent is a common nucleating agent in the art. According to a preferred embodiment of the present invention, the nucleating agent is one or more of a carboxylate nucleating agent, a phosphate nucleating agent and an isosorbide nucleating agent.

[0044] In the present invention, the dispersant is a common dispersant in the art, for example, it can be one or more of stearic acid amide, fatty acid derivatives, and oleic acid amide. According to a preferred embodiment of the present invention, the dispersant is stearic acid amide, and more preferably ethylene bisstearic acid amide (EBS).

[0045] In the present invention, the acid scavenger is a common acid scavenger in the art. According to a preferred embodiment of the present invention, the acid scavenger is one or more of hydrotalcite, calcium stearate and zinc stearate.

[0046] A second aspect of the present invention provides a polybutene-1 / polypropylene alloy material, wherein the polybutene-1 / polypropylene alloy material is prepared from the aforementioned composition.

[0047] In the present invention, the inventors studied the thermal properties of the polybutene-1 / polypropylene alloy material by differential scanning calorimetry (DSC) and found that when the crystallization temperature of the polybutene-1 / polypropylene alloy material is high, the nucleation rate of the alloy material is fast, which is conducive to processing; the inventors also found that the crystallization of the obtained alloy material is multi-distributed, wherein, when the first melting temperature is low and the proportion of the first melting peak melting enthalpy is relatively small, the polybutene-1 / polypropylene alloy material is easy to soften, and the bonding strength of the polypropylene honeycomb tube including the material is high; if the proportion of the first melting peak melting enthalpy is too large, the bonding strength of the polypropylene honeycomb tube including the material is low.

[0048] In the present invention, preferably, the polybutene-1 / polypropylene alloy material has a first crystallization temperature of more than 90°C and a first melting peak melting enthalpy ratio of less than 55% at a heating and cooling rate of 10°C / min. When the first crystallization temperature and the first melting peak melting enthalpy ratio of the material are within the above ranges, the alloy material has a fast solidification rate and is easier to soften at a lower processing temperature (e.g., 120-130°C).

[0049] The third aspect of the present invention provides a method for preparing a polybutene-1 / polypropylene alloy material, the method comprising the following steps: mixing the components of the composition provided by the present invention, feeding the mixed material into a twin-screw machine for extrusion granulation, and stranding and pelletizing.

[0050] 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.

[0051] According to some preferred embodiments of the present invention, in the preparation method, the blending time is 5-30 min, for example, 5 min, 8 min, 12 min, 16 min, 20 min, 25 min, 30 min and any value in the range consisting of any two values, more preferably 8-12 min.

[0052] According to some preferred embodiments of the present invention, in the preparation method, the blending temperature is 200-250°C, for example, 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.

[0053] According to some preferred embodiments of the present invention, in the preparation method, the extrusion temperature is 180-230°C, for example, 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.

[0054] In the present invention, preferably, the composition of the composition is: 100 parts by weight of copolymerized polybutene-1, 20-85 parts by weight of polypropylene, and 0.2-1.4 parts by weight of an auxiliary agent. When each component is within the above range, the resulting polybutene-1 / polypropylene alloy material has a lower melting temperature, a higher crystallization temperature, a low first melting temperature, and a moderate proportion of the first melting peak melting enthalpy; the above material has a fast crystallization rate and good softening properties. More preferably, the composition comprises the following components: 100 parts by weight of copolymerized polybutene-1, 25-80 parts by weight of polypropylene, and 0.4-1 parts by weight of an auxiliary agent. When each component is within the above range, the resulting polybutene-1 / polypropylene alloy material has a faster crystallization rate and better softening properties.

[0055] The fourth aspect of the present invention provides a polybutene-1 / polypropylene alloy material obtained by the aforementioned preparation method.

[0056] In the present invention, preferably, when the polybutene-1 / polypropylene alloy material is measured by differential scanning calorimetry, it satisfies that at a heating and cooling rate of 10°C / min, the first crystallization temperature is above 90°C and the first melting peak melting enthalpy accounts for less than 55%. When the first crystallization temperature and the first melting peak melting enthalpy of the alloy material account for the above range, the alloy material has a fast solidification rate and is easier to soften at a lower processing temperature (e.g., 120-130°C).

[0057] 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.

[0058] In the present invention, preferably, the bonding layer of the polypropylene honeycomb tube comprises the polybutene-1 / polypropylene alloy material provided in the second aspect or the fourth aspect of the present invention.

[0059] In the present invention, preferably, the core layer of the polypropylene honeycomb tube comprises polypropylene.

[0060] In the present invention, when the above-mentioned polybutene-1 / polypropylene alloy material is used as the bonding layer of the polypropylene honeycomb tube, the difficulty of pipe laying is reduced and the processability and processing efficiency are improved; during the hot bonding step, at a lower temperature, for example, at 120-130°C, the bonding layer is easier to soften and the bonding strength of the polypropylene honeycomb tube is greater.

[0061] A sixth aspect of the present invention provides the use of the aforementioned polypropylene honeycomb tube in the preparation of honeycomb panels and composite panels.

[0062] Through the above scheme, the modified polybutene-1 / polypropylene composition provided by the present invention can improve the compatibility of the obtained polybutene-1 / polypropylene alloy material with the core layer polypropylene by virtue of the components it contains, and the crystallization rate is improved, the low melting point component is moderate, and the melting enthalpy of the first melting peak accounts for a small proportion, thereby greatly reducing the difficulty of laying the honeycomb tube including the material and facilitating processing, while being able to maintain a sufficiently high bonding strength.

[0063] The present invention will be described in detail below through examples.

[0064] 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:

[0065] (I) Main raw materials:

[0066] (1) Random copolymerization of polybutene-1:

[0067] 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%;

[0068] 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%;

[0069] (2) Homopolymer polybutene-1:

[0070] Brand PBH-F08, China Petrochemical Corporation Zhenhai Refining and Chemical Company, melting point 128℃, melt index 8g / 10min (190℃ / 2.16kg), crystallization temperature 85℃;

[0071] (3) Ternary random copolymer polypropylene:

[0072] Brand F4908, Maoming Branch of Sinopec, melting point 135°C, melt index 8g / 10min (230°C / 2.16kg), crystallization temperature 107°C, ethylene structural unit content 10mol%, butene structural unit content 1mol%;

[0073] Brand FS6612L, The Polyolefin Company (Singapore) Pte Ltd, melting point 127°C, melt index 35g / 10min (230°C / 2.16kg), crystallization temperature 102°C, content of ethylene structural unit is 6mol%, content of butene structural unit is 6mol%;

[0074] (4) Binary random copolymer polypropylene:

[0075] Brand: M26ET, produced by Zhenhai Refining and Chemical Company of China Petrochemical Corporation, melting point: 152°C, melt index: 26g / 10min (230°C / 2.16kg), crystallization temperature: 130°C, and the content of ethylene structural units: 6 mol%.

[0076] (II) Main equipment:

[0077] (1) Twin-screw extruder: ZSM MAXX, Leistrite, Germany;

[0078] (2) Single screw double-layer tube extruder: Model 65, Qingdao Yasente Machinery Co., Ltd.

[0079] (3) Industrial oven: WD704, Wujiang Wanda Electric Heating Equipment;

[0080] (4) Mechanical properties: 5567 universal testing machine, Instron, USA;

[0081] (5) Thermodynamic testing equipment: DSC, TA Company, USA.

[0082] (III) Test methods:

[0083] (1) Melt index: The melt index of random copolymer polybutene-1 and homopolymer polybutene-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 binary random copolymer polypropylene and ternary random copolymer 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.

[0084] (2) Thermal property test: DSC was used to measure the melting and crystallization characteristics of the polybutene-1 / polypropylene 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 the heating was 220°C, and the lower limit of the cooling was -20°C. The first heating eliminated the thermal history. The melting characteristics of the material were taken from the second heating data, and the crystallization characteristics of the material were taken from the first cooling data.

[0085] (3) Pipe adhesion rate: At an extrusion speed of 280 m / min, the polypropylene honeycomb tube was 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 being stored at room temperature for 30 min, the number of adhered polypropylene honeycomb tubes was manually counted, and finally the percentage of adhered polypropylene honeycomb tubes in the total number of polypropylene honeycomb tubes was calculated.

[0086] (4) Bonding strength test: The honeycomb tube 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.

[0087] (5) The thermal property test, honeycomb tube adhesion rate and bonding strength test results of polybutene-1 / polypropylene alloy material are shown in Table 2 and Table 3.

[0088] Example 1

[0089] The alloy material formula includes:

[0090] Random copolymer polybutene-1, PBR-F08, 100 parts by weight;

[0091] Ternary random copolymer polypropylene, FS6612L, 25 parts by weight;

[0092] Additives: 1.4 parts by weight of antioxidant 1010 / 168, 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.

[0093] The specific preparation method is as follows:

[0094] 1) Preparation of polybutene-1 / polypropylene alloy material:

[0095] The above resin and additives were added into a twin-screw extruder for blending and granulation, the blending time was 10 minutes; 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 / polypropylene alloy material;

[0096] 2) Preparation of polypropylene honeycomb tube:

[0097] The material of the core layer of the polypropylene honeycomb tube is impact-resistant copolymer polypropylene, brand M10RG, from Zhenhai Refining and Chemical Company of China Petrochemical Corporation, melt index: 10g / 10min (230℃ / 2.16kg). The impact-resistant copolymer polypropylene and the above-prepared polybutene-1 / polypropylene alloy material are added to a single-screw double-layer extruder for extrusion molding. The inner layer of the extruder uses impact-resistant copolymer polypropylene, and the outer layer uses the above-prepared polybutene-1 / polypropylene alloy material. 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;

[0098] After the polypropylene honeycomb tube leaves the die, it stays in a 25℃ water tank for 30 seconds, is cut into 400mm lengths, and is arranged in sequence for thermal bonding;

[0099] The neatly arranged honeycomb tubes are placed in an oven with a bonding time of 30 minutes and a bonding temperature of 125°C.

[0100] Example 2-3

[0101] The polybutene-1 / polypropylene 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.

[0102] A polypropylene honeycomb tube was prepared in the same manner as in Example 1, except that the formula of the polybutene-1 / polypropylene alloy material used in the outer layer of the single-screw double-layer extruder was different.

[0103] Comparative Examples 1-8

[0104] The polybutene-1 / polypropylene 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.

[0105] A polypropylene honeycomb tube was prepared in the same manner as in Example 1, except that the formula of the polybutene-1 / polypropylene alloy material used in the outer layer of the single-screw double-layer extruder was different.

[0106] Table 1

[0107]

[0108]

[0109] Test Example 1

[0110] The thermal properties of the polybutene-1 / polypropylene alloy materials prepared in Examples 1-3 and Comparative Examples 1-8 were tested, and the results are shown in Table 2.

[0111] Test Example 2

[0112] The pipe adhesion rate and bonding strength of the polypropylene honeycomb tubes prepared in Examples 1-3 and Comparative Examples 1-8 were tested, and the results are shown in Table 3.

[0113] Table 2

[0114]

[0115] Table 3

[0116]

[0117]

[0118] From the results in Table 2 and Table 3, we can see that:

[0119] Embodiments 1-3 have a higher crystallization temperature and a lower proportion of the first melting peak melting enthalpy, and the prepared honeycomb tubes have a low tube adhesion rate and a high thermal bonding strength.

[0120] In Comparative Example 1, 100 parts by weight of ternary random copolymer polypropylene is added. The amount added is too large, and the melting enthalpy of the first melting peak is too high, resulting in a low softening degree of the bonding layer in the bonding link. Compared with Example 3, the bonding strength of the honeycomb tube is significantly reduced.

[0121] In Comparative Example 2, 15 parts by weight of ternary random copolymer polypropylene is added, but the amount added is too small. Compared with Example 2, the crystallization temperature is too low, the curing rate of the honeycomb tube is slow, the adhesion rate is high, and the tube cannot be laid, which affects the processability of the honeycomb tube.

[0122] Comparative Examples 3 and 4 only added ternary random copolymer polypropylene without random copolymer polybutene-1. Compared with Examples 1-3, the amount of low melting point component was too low, and the bonding strength of the obtained polypropylene honeycomb tubes was significantly reduced.

[0123] Comparative Examples 5 and 6 only added random copolymerized polybutene-1, and the crystallization temperature was too low. Compared with Examples 1-3, the honeycomb tubes had obvious adhesion and lacked processability.

[0124] Comparative Example 7 uses binary random copolymer polypropylene instead of ternary random copolymer polypropylene. The first melting peak temperature of the obtained polybutene-1 / polypropylene alloy material is too high, and the melting enthalpy of the first melting peak accounts for a relatively high proportion, resulting in that the honeycomb tube bonding layer is more difficult to soften during the thermal bonding process. Compared with Example 2, the bonding strength of the honeycomb tube is significantly reduced.

[0125] Comparative Example 8 used homopolymer polybutene-1 instead of random copolymer polybutene-1. The resulting polybutene-1 / polypropylene alloy material had a low proportion of medium and low melting point components, an excessively high second melting peak temperature, and a high proportion of the melting enthalpy of the first melting peak. Compared with Example 2, the bonding strength of the honeycomb tube was significantly reduced.

[0126] 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 appropriate manner, and 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 polybutene-1 / polypropylene composition, characterized in that The composition comprises: 100 parts by weight of copolymerized polybutene-1, 20-85 parts by weight of polypropylene, and 0.2-1.4 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, 25-80 parts by weight of polypropylene, and 0.4-1 part by weight of an auxiliary agent.

3. The composition according to claim 1 or 2, wherein The copolymerized polybutene-1 is a random copolymerized polybutene-1; And / or, the second comonomer of the random copolymer polybutene-1 is ethylene, and the content of the ethylene structural unit is 1-10 mol%, preferably 2-8 mol%, based on the total weight of the random copolymer polybutene-1; And / or, the random copolymer polybutene-1 has a melt index of 8-15 g / 10 min at 190° C. and a load of 2.16 kg; And / or, the melting point of the random copolymerized polybutene-1 is 80-110°C.

4. The composition according to any one of claims 1 to 3, wherein The polypropylene is a random copolymer polypropylene, preferably a ternary random copolymer polypropylene; And / or, the second comonomer of the terpolymer 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 terpolymer random copolymer polypropylene; and / or, the third comonomer is butene; Preferably, the butene is 1-butene; Preferably, based on the total weight of the terpolymer random copolymer polypropylene, the content of the butene structural unit is 0.5-10 mol%, preferably 1-6 mol%; Preferably, the melt index of the terpolymer polypropylene at 230° C. and a load of 2.16 kg is 8-35 g / 10 min; Preferably, the melting point of the terpolymer random copolymer polypropylene is 125-140°C, preferably 127-135°C.

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:(0.5-2.5):(0.2-2.5):(0.1-2); 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 / polypropylene alloy material, characterized in that: The polybutene-1 / polypropylene alloy material is made from the composition described in any one of claims 1 to 5; Preferably, when the polybutene-1 / polypropylene alloy material is measured by differential scanning calorimetry, at a heating and cooling rate of 10°C / min, the first crystallization temperature is above 90°C and the first melting peak melting enthalpy accounts for less than 55%.

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

8. A polybutene-1 / polypropylene alloy material obtained by the preparation method of claim 7; Preferably, when the polybutene-1 / polypropylene alloy material is measured by differential scanning calorimetry, at a heating and cooling rate of 10°C / min, the first crystallization temperature is above 90°C and the first melting peak melting enthalpy accounts for less than 55%.

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 / polypropylene 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 preparing honeycomb panels and composite panels.

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