CN111286128A - Quickly-molded polybutylene resin and preparation method thereof - Google Patents
Quickly-molded polybutylene resin and preparation method thereof Download PDFInfo
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- CN111286128A CN111286128A CN202010223348.2A CN202010223348A CN111286128A CN 111286128 A CN111286128 A CN 111286128A CN 202010223348 A CN202010223348 A CN 202010223348A CN 111286128 A CN111286128 A CN 111286128A
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- polybutene
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- antioxidant
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- 239000011347 resin Substances 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- -1 polybutylene Polymers 0.000 title claims abstract description 30
- 229920001748 polybutylene Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001083 polybutene Polymers 0.000 claims abstract description 52
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 34
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000002667 nucleating agent Substances 0.000 claims abstract description 21
- 239000004595 color masterbatch Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000006096 absorbing agent Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000004611 light stabiliser Substances 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 230000009466 transformation Effects 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 230000003712 anti-aging effect Effects 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- SNAQARSCIHDMGI-UHFFFAOYSA-M sodium;bis(4-tert-butylphenyl) phosphate Chemical compound [Na+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 SNAQARSCIHDMGI-UHFFFAOYSA-M 0.000 claims description 2
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 1
- 239000004594 Masterbatch (MB) Substances 0.000 claims 1
- 150000008430 aromatic amides Chemical class 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention relates to a quickly-formed polybutylene resin and a preparation method thereof, belonging to the field of high polymer materials. The components of the color masterbatch comprise polybutylene, an antioxidant, a halogen absorbing agent, a light stabilizer, a color masterbatch, a nucleating agent and a filler; the preparation method comprises the steps of uniformly mixing the polybutene, the antioxidant, the halogen absorbing agent, the light stabilizer, the color master batch, the nucleating agent and the filler by a high-speed stirring mixer, and carrying out melt extrusion granulation to obtain the polybutene resin. The resin has the characteristics of high crystal form transformation speed, high heat-resistant temperature and the like, and can be used as a cold and hot water pipe material.
Description
Technical Field
The invention relates to a polybutylene resin with rapid crystal form transformation and high thermal deformation temperature, a preparation method and application thereof, belonging to the field of high polymer materials, in particular to the processing and application of the high polymer materials.
Background
The high Isotactic Polybutene (iPB) has outstanding hot creep resistance, environmental stress cracking resistance, high heat resistance temperature and good toughness, and is one of the best materials for the pipe and the connecting piece thereof.
Different from other pipes, the polybutene is melt processed to directly form a metastable crystal form II, and the crystal form II is gradually converted into a stable crystal form I at room temperature. The crystal form of the polybutene is slowly transformed, the transformation time is long (more than 7 days), and in the process of transforming the crystal form, the size of the product is reduced and the strength is increased. Therefore, the polybutene can be transported and applied after being placed at room temperature for more than one week until the crystal form transformation is completed, so that the molding time of the polybutene product is greatly prolonged, and the turnover period of the product is remarkably prolonged. Therefore, the development of a polybutene material with rapid forming (rapid crystal transformation) is of great significance.
CN105273320A discloses a method for adding graphene into polybutene, which accelerates the II-I crystal form transformation of polybutene and improves the mechanical properties of polybutene, but the expensive graphene makes the product have higher cost. The Chinese patent ZL200410032739.7 discloses that acetylene black is used as a nucleating agent to promote the crystal transformation of a 1-butene homopolymer or a 1-butene copolymer and improve the chlorine water resistance of the copolymer. CN104629195B discloses that polybutene in-kettle alloys containing a polypropylene component are prepared by in-kettle polymerization technology, and the crystal form transformation rate can be accelerated. Japanese patent 2618469 discloses that adding propylene homopolymer and HDPE to polybutene shortens the crystal transition period, but the addition of propylene homopolymer and HDPE deteriorates some of its properties.
CN101020777B discloses that a high-thermal-conductivity polybutylene coil pipe is prepared by adding graphite with surface treatment, the pressure resistance and the heat resistance of a product are improved, but the problems of crystal form transformation and rapid forming of polybutylene are not involved. CN105504552B, CN105754233A, and CN1016151774A disclose reinforced polybutylene pipeline material and preparation method thereof, but none of the above patents relate to the problem of rapid molding of polybutylene.
Disclosure of Invention
One of the purposes of the invention is to solve the problem that the crystal form of the polybutene is slowly changed (more than one week), and provide a formula of the polybutene resin for quick forming.
The invention also aims to further improve the heat deformation temperature of the polybutylene resin and improve the heat resistance of the polybutylene resin.
The invention also aims to provide a preparation method of the quick-forming polybutylene resin.
A quickly-formed polybutylene resin comprises the following components in parts by weight:
polybutene 100 parts
0.1-5 parts of antioxidant
0.01-2 parts of halogen absorbing agent
0.01-2 parts of light stabilizer
0.1-5 parts of color masterbatch
0.01-5 parts of nucleating agent
0.1 to 10 portions of filler
The isotactic degree of polybutene in the polybutene resin is more than 96 wt.%, and the melt mass flow rate is 0.2-3g/10min (190 ℃, 2.16 kg). The antioxidant comprises a main antioxidant and an auxiliary antioxidant, the weight ratio of the main antioxidant to the auxiliary antioxidant is 1: 0.5-4, wherein the main antioxidant is selected from one or more of BHT, Hostanox3, 3114, 1010 and 1076, and the auxiliary antioxidant is selected from one or more of 168, 626, 9228, DLTDP, DSTP, DMTDP and DTDTDTP.
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 one or a mixture of two or more of 3, 4-dimethyl benzyl sorbitol, bicyclo [2, 2, 1] disodium heptanedionate, sodium bis (p-tert-butylphenyl) phosphate, aromatic amide compounds and derivatives thereof.
The color master batch comprises the following components in parts by weight: 40-95 parts of high isotactic polybutene (isotacticity greater than 96 wt.%); 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 of an anti-aging agent.
The filler is one or more of calcium carbonate, talcum powder, mica and kaolin.
A preparation method of quickly molded polybutylene resin comprises the following specific preparation steps:
(1) all the raw materials (polybutene, antioxidant, halogen absorbing agent, light stabilizer, color masterbatch, nucleating agent and filler) weighed according to the proportion are uniformly mixed in a high-speed stirring mixer;
(2) adding the uniformly mixed materials in the step (1) into a double-screw extruder with the length-diameter ratio of 30-50: 1, and performing melt extrusion, wherein the extrusion process comprises the following steps: the first zone is 150-.
(3) And (3) granulating and drying the extrudate obtained in the step (2) to obtain the polybutene resin.
The polybutene resin prepared by the invention maintains the excellent shock resistance, excellent heat creep resistance and outstanding environmental stress cracking resistance of polybutene, meanwhile, the crystal form transformation speed is obviously improved, the heat resistance is obviously improved, and the polybutene resin can be used as cold and hot water pipes and pipe fittings.
Detailed Description
The following examples are presented to better illustrate the invention and are not to be construed as limiting the claims of the invention.
The isotactic degree of polybutene in the polybutene alloy resin used was 98. wt%, and the melt flow rate (190 ℃ C., load 2.16kg) was 0.5g/10 min. Measuring the characteristic peak-peak high variation curve of the polybutene crystal form I by using an online infrared spectrum to obtain the t of crystal form conversion1/2And the appearance time of the crystal form I, and the Vicat softening point of the polybutene is measured by a Vicat thermomechanical instrument (GB/T1633-2000A 50 method).
Comparative example 1
Weighing the materials according to the components and the formula (in parts by weight) provided in the table 1, wherein the main antioxidant is 1010 and the auxiliary antioxidant is 168, mixing the materials in a high-speed mixer for 5 minutes, and then extruding and granulating the mixture in a double-screw extruder with the length-diameter ratio of 45 and the diameter of 50 millimeters to obtain the polybutene material. The temperature of each section of the extruder is as follows: 150 ℃ in the first zone, 160 ℃ in the second zone, 170 ℃ in the third zone, 180 ℃ in the fourth zone, 190 ℃ in the fifth zone, 180 ℃ at the head, 20 revolutions per minute at the speed of the extruder and 15MPa of melt pressure.
The results of the performance tests are shown in Table 1.
Example 1
The materials were weighed according to the components and formulations (in parts by weight, the same in the following examples) provided in table 1, wherein the filler was calcium carbonate, the nucleating agent was 3, 4-dimethyldibenzyl sorbitol (nucleating agent 1), the primary antioxidant was 1010, the secondary antioxidant was 168, the halogen absorbing agent was calcium stearate, and the light stabilizer was benzophenone grease. The color master batch (color master 1) comprises the following components in parts by weight: 90 parts of high isotactic polybutene (98 wt.% of isotacticity), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment and 0.03 part of anti-aging agent.
After mixing for 5 minutes in a high-speed stirrer, extruding and granulating in a double-screw extruder with the length-diameter ratio of 45 and the diameter of 50 millimeters to obtain the polybutene resin. The temperature of each section of the extruder is as follows: 150 ℃ in the first zone, 160 ℃ in the second zone, 170 ℃ in the third zone, 180 ℃ in the fourth zone, 190 ℃ in the fifth zone, 180 ℃ at the head, 20 revolutions per minute at the speed of the extruder and 15MPa of melt pressure.
The results of the performance tests are shown in Table 1.
Example 2
The materials are weighed according to the components and the formula (in parts by weight) provided in table 1, wherein the filler is calcium carbonate, the nucleating agent is 3, 4-dimethyl benzyl sorbitol (nucleating agent 1), the main antioxidant is 1010, the auxiliary antioxidant is 168, the halogen absorbing agent is calcium stearate, and the light stabilizer is benzophenone grease. The color master batch (color master 1) comprises the following components in parts by weight: 90 parts of high isotactic polybutene (98 wt.% of isotacticity), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment and 0.03 part of anti-aging agent.
The rest is the same as example 1. The results of the performance tests are shown in Table 1.
Example 3
The materials are weighed according to the components and the formula (in parts by weight) provided in table 1, wherein the filler is calcium carbonate, the nucleating agent is 3, 4-dimethyl benzyl sorbitol (nucleating agent 1), the main antioxidant is 1010, the auxiliary antioxidant is 168, the halogen absorbing agent is calcium stearate, and the light stabilizer is benzophenone grease. The color master batch (color master 2) comprises the following components in parts by weight: 90 parts of high isotactic polybutene (98 wt.% of isotacticity), 1 part of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment and 0.03 part of anti-aging agent.
The rest is the same as example 1. The results of the performance tests are shown in Table 1.
Example 4
The materials were weighed according to the components and formulation (in parts by weight) provided in table 1, wherein the filler was calcium carbonate, the nucleating agent was an aromatic amide compound (nucleating agent 2), the primary antioxidant was 1010, the secondary antioxidant was 168, the halogen absorbing agent was calcium stearate, and the light stabilizer was benzophenone grease. The color master batch (color master 1) comprises the following components in parts by weight: 90 parts of high isotactic polybutene (98 wt.% of isotacticity), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment and 0.03 part of anti-aging agent.
The rest is the same as example 1. The results of the performance tests are shown in Table 1.
Example 5
The materials are weighed according to the components and the formula (in parts by weight) provided in table 1, wherein the filler is calcium carbonate, the nucleating agent is 3, 4-dimethyl benzyl sorbitol (nucleating agent 1), the main antioxidant is 1010, the auxiliary antioxidant is 168, the halogen absorbing agent is calcium stearate, and the light stabilizer is benzophenone grease. The color master batch (color master 1) comprises the following components in parts by weight: 90 parts of high isotactic polybutene (98 wt.% of isotacticity), 3 parts of polypropylene wax, 3 parts of titanium dioxide, 0.01 part of pigment and 0.03 part of anti-aging agent.
After mixing for 5 minutes in a high-speed stirrer, extruding and granulating in a double-screw extruder with the length-diameter ratio of 45 and the diameter of 50 millimeters to obtain the polybutene resin. The temperature of each section of the extruder is as follows: 155 ℃ in the first zone, 165 ℃ in the second zone, 175 ℃ in the third zone, 185 ℃ in the fourth zone, 195 ℃ in the fifth zone, 185 ℃ in the head, 25 revolutions per minute in the extruder and 15MPa in the melt pressure.
The results of the performance tests are shown in Table 1.
As can be seen from the results of the examples and comparative example 1, the crystal transformation speed of the polybutene resin of the present invention is greatly increased as compared with polybutene, and the heat resistance can be increased by 7.1 ℃.
TABLE 1 Components and formulations of the examples and comparative examples
| Components | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Polybutene/part by weight | 100 | 100 | 100 | 100 | 100 | 100 |
| Fillers/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/part by weight | 0 | 0 | 0 | 0.3 | 0 | 0 |
| Main antioxidant per weight portion | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Auxiliary antioxidant/part by weight | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Halogen-absorbing agent/part by weight | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0 |
| Light stabilizer per part by weight | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0 |
| 1 part by weight of color master batch | 2 | 2 | 0 | 2 | 2 | 0 |
| 2 parts by weight of color master batch | 0 | 0 | 2 | 0 | 0 | 0 |
| T of crystal form transformation1/2Hour/hour | 15.9 | 15.6 | 15.9 | 21.2 | 18.2 | 58.4 |
| Time of appearance/hour of form I | 3.0 | 2.8 | 3.0 | 4.1 | 3.6 | 19.7 |
| Vicat softening point/. degree C | 121.5 | 120.9 | 120.1 | 118.8 | 119.8 | 114.4 |
Claims (10)
1. A polybutylene resin for rapid prototyping is characterized by comprising the following components in parts by weight:
polybutene 100 parts
0.1-5 parts of antioxidant
0.01-2 parts of halogen absorbing agent
0.01-2 parts of light stabilizer
0.1-5 parts of color masterbatch
0.01-5 parts of nucleating agent
0.1-10 parts of filler.
2. A fast-forming polybutene resin as claimed in claim 1, wherein the polybutene in the polybutene resin has an isotacticity of more than 96 wt.%, a melt mass flow rate of 0.2-3g/10min at 2.16kg at 190 ℃.
3. The polybutylene resin with the rapid prototyping function according to any one of claims 1 or 2, wherein the antioxidant is composed of a main antioxidant and a secondary antioxidant, the weight ratio of the main antioxidant to the secondary antioxidant is 1: 0.5-4, wherein the main antioxidant is selected from one or more of BHT, Hostanox3, 3114, 1010 and 1076, and the secondary antioxidant is selected from one or more of 168, 626, 9228, DLTDP, DSTP, DMTDP and DTDTDTDTP.
4. A fast-forming polybutene resin as claimed in claim 1 or 2, wherein the halogen-absorbing agent is one or more of hydrotalcite, calcium stearate, sodium stearate or zinc stearate.
5. The polybutylene resin for rapid prototyping according to any of claims 1 or 2, wherein the light stabilizer is one or more of benzophenones and hindered amines.
6. The polybutene resin as claimed in claim 1 or 2, wherein the nucleating agent is one or a mixture of two or more of 3, 4-dimethyldibenzyl sorbitol, disodium bicyclo [2, 2, 1] heptanedionate, sodium bis (p-tert-butylphenyl) phosphate, aromatic amides and their derivatives.
7. A fast-forming polybutene resin as claimed in claims 1 or 2, wherein the masterbatch comprises the following components in parts by weight: 40-95 parts of high isotactic polybutene (isotacticity greater than 96 wt.%); 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 of an anti-aging agent.
8. A polybutene resin as claimed in claim 1 or 2, wherein the filler is one or more of calcium carbonate, talc, mica and kaolin.
9. A preparation method of quickly-formed polybutylene resin is characterized by comprising the following specific preparation steps:
(1) all the raw materials (polybutene, antioxidant, halogen absorbing agent, light stabilizer, color masterbatch, nucleating agent and filler) weighed according to the proportion are uniformly mixed in a high-speed stirring mixer;
(2) adding the uniformly mixed materials in the step (1) into a double-screw extruder with the length-diameter ratio of 30-50: 1, and performing melt extrusion, wherein the extrusion process comprises the following steps: the first zone is 150-;
(3) and (3) granulating and drying the extrudate obtained in the step (2) to obtain the polybutene resin.
10. The polybutene resin as claimed in claim 1 or 2, wherein the polybutene resin has a high transformation rate of crystal form and high heat-resistant temperature, and is used as a material for hot and cold water pipes.
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| CN111286128B (en) | 2023-02-10 |
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