CN111286128B - A kind of rapid prototyping polybutene resin and preparation method thereof - Google Patents

Abstract

The invention relates to a rapidly prototyping polybutene resin and a preparation method thereof, belonging to the field of polymer materials. Its components include polybutene, antioxidant, halogen absorbing agent, light stabilizer, color masterbatch, nucleating agent, filler; the preparation method is to mix polybutene, antioxidant, halogen absorbing agent, light stabilizer, The color masterbatch, nucleating agent and filler are uniformly mixed with a high-speed mixing mixer, melted and extruded to obtain polybutene resin. The resin has the characteristics of fast crystal transformation speed and high heat resistance temperature, and can be used as a material for cold and hot water pipes.

Description

A kind of rapid prototyping polybutene resin and preparation method thereof

technical field

The invention relates to a polybutene resin with rapid crystal transformation and high heat distortion temperature, a preparation method and application thereof, and belongs to the field of polymer materials, especially the processing and application of polymer materials.

Background technique

High isotactic polybutene (iPB) has outstanding thermal creep resistance, environmental stress cracking resistance, high heat resistance temperature, and good toughness. It is one of the best materials for pipes and their connectors.

Unlike other pipes, polybutene is melt-processed directly to form metastable form II, which gradually transforms into stable form I at room temperature. The crystal form transformation of polybutene is slow, and the transformation time is longer (greater than 7 days). During the crystal form transformation process, the product size shrinks and the strength increases. Therefore, polybutene needs to be placed at room temperature for more than a week until the crystal transformation is completed before it can be transported and applied after melt processing, which greatly increases the molding time of polybutene products and significantly increases the turnover cycle of products. Therefore, it is of great significance to develop a rapid prototyping (fast crystal transformation) polybutene material.

CN105273320A discloses a method for adding graphene to polybutene, which accelerates the II-I crystal transformation of polybutene and improves the mechanical properties of polybutene, but expensive graphene makes the cost of the product higher. Chinese invention patent ZL200410032739.7 discloses the use of acetylene black as a nucleating agent to promote the crystal transformation of 1-butene homopolymer or 1-butene copolymer and improve its resistance to chlorine water. CN104629195B discloses that a polybutene in-kettle alloy containing polypropylene components is prepared by in-kettle polymerization technology, which can accelerate the crystal transformation rate. Japanese Patent No. 2618469 discloses adding propylene homopolymer and HDPE to polybutene to shorten the crystal transformation period, but the addition of propylene homopolymer and HDPE makes some properties worse.

CN101020777B discloses that a polybutene coil with high thermal conductivity is prepared by adding surface-treated graphite, which improves the pressure resistance and heat resistance of the product, but does not involve the crystal transformation and rapid prototyping of polybutene. CN105504552B, CN105754233A, and CN1016151774A disclose reinforced polybutene pipe materials and preparation methods thereof, but none of the above patents involves the rapid prototyping of polybutene.

Contents of the invention

One of the purposes of the present invention is to solve the slow crystal transformation of polybutene (more than one week), and provide a formula for rapid prototyping of polybutene resin.

The second object of the present invention is to further increase the heat distortion temperature of the polybutene resin and improve its heat resistance.

The third object of the present invention is to provide a preparation method of rapid prototyping polybutene resin.

A rapid prototyping polybutene resin, consisting of the following components in parts by weight:

Polybutene 100 parts

Antioxidant 0.1-5 parts

Halogen absorbing agent 0.01-2 parts

Light stabilizer 0.01-2 parts

Color masterbatch 0.1-5 parts

Nucleating agent 0.01-5 parts

Filler 0.1-10 parts

The isotacticity of polybutene in the polybutene resin is greater than 96wt.%, and the melt mass flow rate is 0.2-3g/10min (190°C, 2.16kg). The antioxidant is composed of a main antioxidant and an auxiliary antioxidant, the weight ratio of the main antioxidant and the auxiliary antioxidant is 1:0.5～4, wherein the main antioxidant is selected from BHT, Hostanox3, 3114, 1010 , one or more of 1076, the auxiliary antioxidant is selected from one or more of 168, 626, 9228, DLTDP, DSTP, DMTDP, DTDTP.

The halogen-absorbing agent is one or more of hydrotalcite, calcium stearate, sodium stearate or zinc stearate.

The light stabilizer is one or more of benzophenones or hindered amines.

The nucleating agent is 3,4-dimethylbenzyl sorbitol, disodium bicyclo[2,2,1]heptanedicarboxylate, bis(p-tert-butylphenyl)sodium phosphate, aromatic One or two or more kinds of amide compounds and their derivatives are mixed.

The color masterbatch includes the following components by weight: 40-95 parts of high isotactic polybutene (isotacticity greater than 96wt.%); 0.1-6 parts of polyethylene wax or polypropylene wax; 0.1-6 parts Titanium dioxide; 0.001-6 parts of pigment; 0.01-3 parts of anti-aging agent.

The filler is one or more of calcium carbonate, talcum powder, mica and kaolin.

A preparation method of a rapidly prototyping polybutene resin, the specific preparation steps comprising:

(1) The raw materials (polybutene, antioxidant, halogen absorbing agent, light stabilizer, color masterbatch, nucleating agent, filler) weighed in proportion are mixed uniformly in a high-speed mixer;

(2) Add the homogeneously mixed material in step (1) into a twin-screw extruder with an aspect ratio of 30-50:1, and melt and extrude. The extrusion process is: 150-160°C in the first zone, 160- 170°C, 170-180°C in the third zone, 180-190°C in the fourth zone, 190-210°C in the fifth zone, 180-200°C at the head, 5-30r/min rotating speed, and 10-20MPa melt pressure.

(3) Granulating and drying the extruded product of step (2) to obtain polybutene resin.

The polybutene resin prepared by the invention maintains the excellent impact resistance, excellent thermal creep resistance, and outstanding environmental stress cracking resistance of polybutene, and at the same time, the crystal transformation speed is significantly improved, and the heat resistance is significantly improved. It can be used as Hot and cold water pipes and fittings.

Detailed ways

The following examples are for better explaining the present invention, but do not limit the claims of the present invention.

The isotacticity of polybutene in the polybutene alloy resin used was 98.wt%, and its melt flow rate (190°C, load 2.16kg) was 0.5g/10min. Adopt on-line infrared spectrometry to measure polybutene crystal form I characteristic peak peak height variation curve to obtain the t _1/2 of crystal form transformation and the time that crystal form I appears, adopt the Vicat softening point ( GB/T1633-2000 A50 method).

Comparative example 1

Weigh the material according to the components and formulas provided in Table 1 (according to parts by weight), wherein the main antioxidant is 1010, and the auxiliary antioxidant is 168. After mixing in a high-speed mixer for 5 minutes, the aspect ratio is 45, the diameter Extrude and granulate in a 50 mm twin-screw extruder to obtain polybutene material. The temperature of each zone of the extruder is: 150°C in zone 1, 160°C in zone 2, 170°C in zone 3, 180°C in zone 4, 190°C in zone 5, 180°C at the head, 20 rpm of extruder, melt pressure 15MPa.

The performance test results are shown in Table 1.

Example 1

The components and formulas provided in Table 1 (according to parts by weight, the following examples are the same) take the material, wherein the filler is calcium carbonate, and the nucleating agent is 3,4-dimethylbenzylsorbitol (nucleating agent 1), the main antioxidant is 1010, the secondary antioxidant is 168, the halogen absorbing agent is calcium stearate, and the light stabilizer is benzophenone resin. Color masterbatch (color masterbatch 1) contains the following components by weight: 90 parts of high isotactic polybutene (isotacticity 98wt.%), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment, 0.03 part Antiaging agent.

After mixing in a high-speed mixer for 5 minutes, extrude and granulate in a twin-screw extruder with an aspect ratio of 45 and a diameter of 50 mm to obtain a polybutene resin. The temperature of each zone of the extruder is: 150°C in zone 1, 160°C in zone 2, 170°C in zone 3, 180°C in zone 4, 190°C in zone 5, 180°C at the head, 20 rpm of extruder, melt pressure 15MPa.

The performance test results are shown in Table 1.

Example 2

The components and formula (according to parts by weight) provided by Table 1 weigh materials, wherein the filler is calcium carbonate, and the nucleating agent is 3,4-dimethylbenzyl sorbitol (nucleating agent 1), the main antibiotic The oxygen agent is 1010, the secondary antioxidant is 168, the halogen absorbing agent is calcium stearate, and the light stabilizer is benzophenone resin. Color masterbatch (color masterbatch 1) contains the following components by weight: 90 parts of high isotactic polybutene (isotacticity 98wt.%), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment, 0.03 part Antiaging agent.

Others are the same as embodiment 1. The performance test results are shown in Table 1.

Example 3

The components and formula (according to parts by weight) provided by Table 1 weigh materials, wherein the filler is calcium carbonate, and the nucleating agent is 3,4-dimethylbenzyl sorbitol (nucleating agent 1), the main antibiotic The oxygen agent is 1010, the secondary antioxidant is 168, the halogen absorbing agent is calcium stearate, and the light stabilizer is benzophenone resin. Color masterbatch (color masterbatch 2) contains the following components by weight: 90 parts of high isotactic polybutene (isotacticity 98wt.%), 1 part of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment, 0.03 part Antiaging agent.

Others are the same as embodiment 1. The performance test results are shown in Table 1.

Example 4

The component and formula (according to parts by weight) provided by table 1 take by weighing material, and wherein filler is calcium carbonate, and nucleating agent is aromatic amide compound (nucleating agent 2), and main antioxidant is 1010, auxiliary antioxidant is 168, the halogen-absorbing agent is calcium stearate, and the light stabilizer is benzophenone resin. Color masterbatch (color masterbatch 1) contains the following components by weight: 90 parts of high isotactic polybutene (isotacticity 98wt.%), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment, 0.03 part Antiaging agent.

Others are the same as embodiment 1. The performance test results are shown in Table 1.

Example 5

The components and formula (according to parts by weight) provided by Table 1 weigh materials, wherein the filler is calcium carbonate, and the nucleating agent is 3,4-dimethylbenzyl sorbitol (nucleating agent 1), the main antibiotic The oxygen agent is 1010, the secondary antioxidant is 168, the halogen absorbing agent is calcium stearate, and the light stabilizer is benzophenone resin. Color masterbatch (color masterbatch 1) contains the following components by weight: 90 parts of high isotactic polybutene (isotacticity 98wt.%), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment, 0.03 part Antiaging agent.

After mixing in a high-speed mixer for 5 minutes, extrude and granulate in a twin-screw extruder with an aspect ratio of 45 and a diameter of 50 mm to obtain a polybutene resin. The temperature of each section of the extruder is: 155°C in zone 1, 165°C in zone 2, 175°C in zone 3, 185°C in zone 4, 195°C in zone 5, 185°C at the head, extruder speed 25 rpm, melt pressure 15MPa.

The performance test results are shown in Table 1.

From the results of Examples and Comparative Example 1, it can be seen that the crystal transformation rate of the polybutene resin of the present invention is significantly higher than that of polybutene, and the heat resistance can be increased by 7.1°C.

Component and formula of table 1 embodiment and comparative example

components Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Polybutene/weight part 100 100 100 100 100 100 Filler/parts by weight 5 5 5 5 5 0 Nucleating agent 1/part by weight 0.3 0.5 0.3 0 0.3 0 Nucleating agent 2/parts by weight 0 0 0 0.3 0 0 Primary antioxidant/weight part 0.1 0.1 0.1 0.1 0.1 0.1 Auxiliary antioxidant/weight part 0.2 0.2 0.2 0.2 0.2 0.2 Halogen absorbent/parts by weight 0.1 0.1 0.1 0.1 0.1 0 Light stabilizer/parts by weight 0.8 0.8 0.8 0.8 0.8 0 Masterbatch 1/part by weight 2 2 0 2 2 0 Masterbatch 2/parts by weight 0 0 2 0 0 0 t_1/2/hour of crystal transformation 15.9 15.6 15.9 21.2 18.2 58.4 Form I appearance time/hour 3.0 2.8 3.0 4.1 3.6 19.7 Vicat softening point/℃ 121.5 120.9 120.1 118.8 119.8 114.4

Claims (6)

1. a polybutene resin for rapid prototyping, is characterized in that, is made up of the component of following weight fraction: Polybutene 100 parts Antioxidant 0.1-5 parts Halogen absorbing agent 0.01-2 parts Light stabilizer 0.01-2 parts Color masterbatch 0.1-5 parts Nucleating agent 0.01-5 parts 0.1-10 parts of filler; Wherein, the isotacticity of the polybutene is greater than 96wt.%, 190 ^o C, and the melt mass flow rate under 2.16kg is 0.2-3g/10min; the color masterbatch includes the following components by weight: 40 -95 parts of high isotactic polybutene whose isotacticity is greater than 96wt.%; 0.1-6 parts of polyethylene wax or polypropylene wax; 0.1-6 parts of titanium dioxide; 0.001-6 parts of pigment; 0.01-3 parts anti-aging agent; the nucleating agent is 3,4-dimethylbenzylidene sorbitol; Described polybutene resin adopts following steps to prepare: (1) The raw materials weighed in proportion are mixed evenly in a high-speed mixer; (2) Put the homogeneously mixed materials in step (1) into a twin-screw extruder with an aspect ratio of 45:1, and melt extrude. The extrusion process is: 150 ^o C in the first zone, 160 ^o C in the second zone, and Zone 170 ^o C, zone four 180 ^o C, zone five 190 ^o C, head 180 ^o C, speed 20r/min, melt pressure 15 MPa; (3) Granulating and drying the extruded product of step (2) to obtain polybutene resin; or Described polybutene resin adopts following steps to prepare: (1) The raw materials weighed in proportion are mixed evenly in a high-speed mixer; (2) Put the homogeneously mixed materials in step (1) into a twin-screw extruder with an aspect ratio of 45:1, and melt extrude. The extrusion process is: 155 ^o C in the first zone, 165 ^o C in the second zone, and Zone 175 ^o C, zone four 185 ^o C, zone five 195 ^o C, head 185 ^o C, speed 25r/min, melt pressure 15 MPa; (3) Granulating and drying the extruded product in step (2) to obtain a polybutene resin. 2. a kind of polybutene resin of rapid prototyping according to claim 1, is characterized in that, described antioxidant is made up of main antioxidant and auxiliary antioxidant, and the main antioxidant and auxiliary antioxidant The weight ratio is 1:0.5~4, wherein the main antioxidant is selected from one or more of BHT, Hostanox3, 3114, 1010, 1076, and the auxiliary antioxidant is selected from 168, 626, 9228, DLTDP, DSTP, DMTDP , One or more of DTDTP. 3. a kind of rapidly prototyping polybutene resin according to claim 1, is characterized in that, described halogen absorbing agent is a kind of in hydrotalcite, calcium stearate, sodium stearate or zinc stearate or several. 4. A kind of rapid prototyping polybutene resin according to claim 1, characterized in that, the light stabilizer is one or more of benzophenones or hindered amines. 5. a kind of rapid prototyping polybutene resin according to claim 1 is characterized in that, described filler is one or more in calcium carbonate, talcum powder, mica, kaolin. 6. A kind of rapid prototyping polybutene resin according to claim 1, characterized in that the polybutene resin has characteristics such as fast crystal transformation speed and high heat resistance temperature, and can be used as cold and hot water pipe material.