CN112457448A - LDPE polymer with high temperature resistance and high performance and preparation method thereof - Google Patents

LDPE polymer with high temperature resistance and high performance and preparation method thereof Download PDF

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Publication number
CN112457448A
CN112457448A CN202011354696.XA CN202011354696A CN112457448A CN 112457448 A CN112457448 A CN 112457448A CN 202011354696 A CN202011354696 A CN 202011354696A CN 112457448 A CN112457448 A CN 112457448A
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ldpe
high temperature
temperature resistance
high performance
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解朝辉
解洪俊
孙伟明
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Jiangsu Baoyuan Gaoxin Electric Co ltd
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Jiangsu Baoyuan Gaoxin Electric Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms

Abstract

The invention discloses a high-temperature-resistant high-performance LDPE polymer and a preparation method thereof, wherein the LDPE polymer is prepared from the following components in parts by weight: 100 parts of LDPE, 5-8 parts of 2-acrylic acid (1-methylethylene) bis (4, 1-phenyleneoxy-2, 1-ethanediyl) ester, 2-5 parts of 1, 4-bis- [ 4- (6-acryloyloxy hexyloxy) benzoyloxy ] -2-methylbenzene, 0.2-0.5 part of N, N-diisopropylethanolamine, 0.25-0.5 part of DCP, 0.6-1.0 part of lubricant and 10100.1-0.2 part of antioxidant. The invention can not only improve the high temperature resistance of LDPE, but also improve the physical and mechanical properties and stress fission resistance of LDPE; meanwhile, the impact resistance and the flame retardant property are improved to a certain degree, and the application range of the flame retardant is expanded.

Description

LDPE polymer with high temperature resistance and high performance and preparation method thereof
Technical Field
The invention belongs to the technical field of high molecular materials, and particularly relates to a high-temperature-resistant high-performance LDPE polymer and a preparation method thereof.
Background
LDPE (low density polyethylene) is a general thermoplastic high polymer material, has good physical and mechanical properties, and is widely applied to the aspects of food, packaging, household appliances, daily necessities and the like. However, the LDPE material has disadvantages of low heat resistance, low hardness at high temperature, easy yield deformation, etc., and thus the application range is limited to a large extent.
Disclosure of Invention
The invention aims to overcome the defects and provide the LDPE polymer with high temperature resistance and high performance.
Another object of the present invention is to provide a process for preparing the high temperature resistant high performance LDPE polymer.
The purpose of the invention is realized by the following modes:
the LDPE polymer with high temperature resistance and high performance is prepared from the following components in parts by weight:
Figure BDA0002802285710000011
preferably, the LDPE polymer is prepared from the following components in parts by weight:
Figure BDA0002802285710000021
preferably, the lubricant is EBS.
Preferably, the antioxidant is antioxidant 1010.
LDPE is low density polyethylene; DCP is dicumyl peroxide.
The preparation method of the LDPE polymer with high temperature resistance and high performance comprises the following steps: (1) extruding on a double-screw extruder with the length-diameter ratio L/D (48), wherein the double-screw extruder is provided with twelve sections and 3 feed inlets, the first feed inlet is positioned at the first section of the extruder, the second feed inlet is positioned at the fifth section of the extruder, and the third feed inlet is positioned at the seventh section of the extruder.
(2) LDPE was added to the first feed port of a twin screw extruder running at 120 r/min.
(3) After uniformly mixing 1-methylethylidene diacrylate, bis (4, 1-phenylene oxy-2, 1-2 diyl) ester, 1, 4-bis- [ 4- (6-acryloxyhexyloxy) benzoyloxy ] -2-methylbenzene DCP, a catalyst and N, N-diisopropylethanolamine according to a formula proportion, adding the mixture into a second feeding hole of a double-screw extruder. The grafting reaction of the LDPE molecular chain occurs, and the processing temperature of the extruder is gradually increased from 90-100 ℃ in the first section to 210-220 ℃ in the seventh section. The extrusion temperature of the tail section of the extruder is gradually reduced to 160-170 ℃.
(4) Mixing the lubricant and the antioxidant, and adding the mixture into a third feeding port of the extruder; wherein, the process temperature of each section is as follows: a first section: 90 ℃ to 100 ℃, second zone: 150 ℃ to 160 ℃, and a third section: 170 ℃ to 180 ℃, fourth zone: 180 ℃ to 190 ℃, fifth zone: 190 ℃ to 200 ℃, sixth section: 200 ℃ to 210 ℃, seventh zone: 210 ℃ to 220 ℃, eighth section: 200 ℃ to 210 ℃, ninth zone: 190 ℃ to 200 ℃, tenth section: 180 ℃ to 190 ℃, eleventh section: 180 ℃ to 190 ℃, twelfth zone: 160-170 ℃.
Preferably the LDPE feed rate is 95 kg/h.
Preferably, the operation rate of the twin-screw extruder in the step (2) is 120 r/min.
Preferably, the feeding conditions of the second feeding hole are as follows: feeding at a feeding rate of 6.5kg/h under a pressure of 1.2-1.5 MPa.
The feed rate of the third feed port is preferably 0.45 kg/h.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, in the LDPE extrusion process, a functional monomer containing phenylene group is added: 1-methylethylidene) bis (4, 1-phenyleneoxy-2, 1-ethanediyl) 2-propenoate and another functional monomer having a synergistic effect comprising a benzoyl group: 1, 4-bis- [ 4- (6-acryloyloxy hexyloxy) benzoyloxy ] -2-methylbenzene is subjected to a grafting reaction on an LDPE molecular chain under the action of an initiator DCP and a catalyst N, N-diisopropylethanolamine. The grafted LDPE has the advantages that 2-acrylic acid (1-methylethylene) di (4, 1-phenylene oxy-2, 1-ethanediyl ester containing phenylene groups and 1, 4-bis (4- (6-acryloxyhexyloxy) benzoyloxy) -2-methylbenzene containing benzoyl groups are introduced into the molecular chain of the grafted LDPE, so that the molecular steric hindrance of the LDPE is larger, and the energy required by the whole molecular activity is increased, so that the high-temperature resistance of the LDPE is improved, the physical and mechanical properties of the LDPE and the stress fission resistance of the LDPE are improved to a certain extent, and the application range of the LDPE is expanded.
Detailed Description
The invention is further illustrated and described below by means of specific examples: wherein, the 2-acrylic acid (1-methylethylidene) bis (4, 1-phenyleneoxy-2, 1-ethanediyl) ester is purchased from Guanao biotechnology limited in Hubei, and the 1, 4-bis- [ 4- (6-acryloxyhexyloxy) benzoyloxy ] -2-methylbenzene is purchased from Xinkang pharmaceutical chemical limited in Hubei; n, N-diisopropylethanolamine is purchased from Shanghai Jingyan chemical technology Co., Ltd; n-phenyl maleimide is available from Merrel chemical technology, Inc., Shanghai.
Example 1
Figure BDA0002802285710000031
The preparation method comprises the following steps:
(1) extruding on a double-screw extruder with the length-diameter ratio L/D (48), wherein the double-screw extruder is provided with twelve sections and 3 feed inlets, the first feed inlet is positioned at the first section of the extruder, the second feed inlet is positioned at the fifth section of the extruder, and the third feed inlet is positioned at the seventh section of the extruder.
(2) LDPE was fed at a feed rate of 95kg/h into a twin-screw extruder running at 120r/min at the first feed opening.
(3) After 2-acrylic acid (1-methylethylidene) bis (4, 1-phenyleneoxy-2, 1-ethanediyl) ester, 1, 4-bis- [ 4- (6-acryloxyhexyloxy) benzoyloxy ] -2-methylbenzene, DCP and a catalyst N, N-diisopropylethanolamine are uniformly mixed according to a formula proportion, the mixture is added into a second feed inlet of a double-screw extruder at a feed rate of 6.5kg/h under the pressure of 1.2-1.5 MPa, the grafting reaction of LDPE molecular chains occurs, and the processing temperature of the extruder is gradually increased from 90-100 ℃ in a section 1 to 210-220 ℃ in a section seven. The extrusion temperature of the tail section of the extruder is gradually reduced to 160-170 ℃.
(4) EBS lubricant and antioxidant 1010 were mixed and fed into the third feed port of the extruder at a feed rate of 0.45 kg/h. The process temperatures in each section were as follows: a first section: 90 ℃ to 100 ℃, second zone: 150 ℃ to 160 ℃, and a third section: 170 ℃ to 180 ℃, fourth zone: 180 ℃ to 190 ℃, fifth zone: 190 ℃ to 200 ℃, sixth section: 200 ℃ to 210 ℃, seventh zone: 210 ℃ to 220 ℃, eighth section: 200 ℃ to 210 ℃, ninth zone: 190 ℃ to 200 ℃, tenth section: 180 ℃ to 190 ℃, eleventh section: 180 ℃ to 190 ℃, twelfth zone: 160-170 ℃.
Example 2
Figure BDA0002802285710000041
The preparation method comprises the following steps:
(1) extruding on a double-screw extruder with the length-diameter ratio L/D (48), wherein the double-screw extruder is provided with twelve sections and 3 feed inlets, the first feed inlet is positioned at the first section of the extruder, the second feed inlet is positioned at the fifth section of the extruder, and the third feed inlet is positioned at the seventh section of the extruder.
(2) LDPE was fed at a feed rate of 95kg/h into a twin-screw extruder running at 120r/min at the first feed opening.
(3) After 2-acrylic acid (1-methylethylidene) bis (4, 1-phenyleneoxy-2, 1-ethanediyl) ester, 1, 4-bis- [ 4- (6-acryloxyhexyloxy) benzoyloxy ] -2-methylbenzene, DCP and a catalyst N, N-diisopropylethanolamine are uniformly mixed according to a formula proportion, the mixture is added into a second feed inlet of a double-screw extruder at a feed rate of 6.5kg/h under the pressure of 1.2-1.5 MPa, the grafting reaction of LDPE molecular chains occurs, and the processing temperature of the extruder is gradually increased from 90-100 ℃ in a section 1 to 210-220 ℃ in a section seven. The extrusion temperature of the tail section of the extruder is gradually reduced to 160-170 ℃.
(4) EBS lubricant and antioxidant 1010 were mixed and fed into the third feed port of the extruder at a feed rate of 0.45 kg/h. The process temperatures in each section were as follows: a first section: 90 ℃ to 100 ℃, second zone: 150 ℃ to 160 ℃, and a third section: 170 ℃ to 180 ℃, fourth zone: 180 ℃ to 190 ℃, fifth zone: 190 ℃ to 200 ℃, sixth section: 200 ℃ to 210 ℃, seventh zone: 210 ℃ to 220 ℃, eighth section: 200 ℃ to 210 ℃, ninth zone: 190 ℃ to 200 ℃, tenth section: 180 ℃ to 190 ℃, eleventh section: 180 ℃ to 190 ℃, twelfth zone: 160-170 ℃.
Comparative example 1:
the method for adding the heat-resistant modifier comprises the following steps: n-phenylmaleimide.
Figure BDA0002802285710000051
The heat resistant modifier was added to the second feed port of the twin screw extruder and the rest of the twin screw extrusion techniques were the same as in example 1.
The product of example 1 and the product of comparative example were subjected to performance tests, the results of which are shown in Table 1:
TABLE 1
Figure BDA0002802285710000052
Figure BDA0002802285710000061
And (3) testing the thermal aging performance according to GB/T3512-2001 test conditions: the test temperature is 100 +/-2 ℃, and the time is as follows: 168 hours, the test results are shown in Table 2.
TABLE 2
Figure BDA0002802285710000062
Figure BDA0002802285710000071

Claims (9)

1. The LDPE polymer with high temperature resistance and high performance is characterized by being prepared from the following components in parts by weight:
Figure FDA0002802285700000011
2. the LDPE polymer with high temperature resistance and high performance according to claim 1, characterized in that the LDPE polymer is prepared from the following components in parts by weight:
Figure FDA0002802285700000012
3. the high temperature resistant high performance LDPE polymer according to claim 1 or 2 wherein said lubricant is EBS.
4. The LDPE polymer with high temperature resistance and high performance according to claim 1 or 2, wherein the antioxidant is antioxidant 1010.
5. A process for the preparation of LDPE polymer having high temperature resistance and high performance as claimed in claim 1, characterized in that it comprises the following steps:
(1) extruding on a double-screw extruder with the length-diameter ratio L/D (equal to 48), wherein the double-screw extruder is provided with twelve sections and 3 feed inlets, the first feed inlet is positioned at the first section of the extruder, the second feed inlet is positioned at the fifth section of the extruder, and the third feed inlet is positioned at the seventh section of the extruder;
(2) adding LDPE into a first feed port of a double-screw extruder;
(3) uniformly mixing 1-methylethylidene diacrylate, bis (4, 1-phenylene oxy-2, 1-2 diyl) diacrylate, 1, 4-bis- [ 4- (6-acryloyloxy hexyloxy) benzoyloxy ] -2-methylbenzene DCP and a catalyst N, N-diisopropylethanolamine according to a formula ratio, and adding the mixture into a second feed port of a double-screw extruder;
(4) mixing the lubricant and the antioxidant, and adding the mixture into a third feeding port of the extruder; wherein, the process temperature of each section is as follows: a first section: 90 ℃ to 100 ℃, second zone: 150 ℃ to 160 ℃, and a third section: 170 ℃ to 180 ℃, fourth zone: 180 ℃ to 190 ℃, fifth zone: 190 ℃ to 200 ℃, sixth section: 200 ℃ to 210 ℃, seventh zone: 210 ℃ to 220 ℃, eighth section: 200 ℃ to 210 ℃, ninth zone: 190 ℃ to 200 ℃, tenth section: 180 ℃ to 190 ℃, eleventh section: 180 ℃ to 190 ℃, twelfth zone: 160-170 ℃.
6. The method for preparing LDPE polymer with high temperature resistance and high performance according to claim 1, characterized in that the LDPE feeding speed is 95 kg/h.
7. The method for preparing LDPE polymer with high temperature resistance and high performance according to claim 1, wherein the operation speed of the twin-screw extruder in step (2) is 120 r/min.
8. The method for preparing the LDPE polymer with high temperature resistance and high performance according to claim 1, characterized in that the feeding at the second feed inlet adopts the following conditions: feeding at a feeding rate of 6.5kg/h under a pressure of 1.2-1.5 MPa.
9. The method for preparing LDPE polymer with high temperature resistance and high performance according to claim 1, wherein the feeding rate of the third feeding port is 0.45 kg/h.
CN202011354696.XA 2020-11-26 2020-11-26 LDPE polymer with high temperature resistance and high performance and preparation method thereof Pending CN112457448A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113234298A (en) * 2021-06-10 2021-08-10 江苏宝源高新电工有限公司 High-performance LDPE ionic polymer and preparation method thereof
CN113667258A (en) * 2021-08-24 2021-11-19 江苏宝安电缆有限公司 High-strength super-toughness HDPE polymer and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591017A (en) * 2019-08-12 2019-12-20 无锡市宇盛线缆有限公司 High-performance epoxy resin and grafting reaction method thereof
CN111848875A (en) * 2020-06-19 2020-10-30 江苏益帆高分子材料有限公司 Antibacterial LDPE produced by grafting reaction extrusion and preparation process thereof
CN111909481A (en) * 2020-07-20 2020-11-10 江苏宝安电缆有限公司 Antibacterial LDPE produced by grafting reactive extrusion and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591017A (en) * 2019-08-12 2019-12-20 无锡市宇盛线缆有限公司 High-performance epoxy resin and grafting reaction method thereof
CN111848875A (en) * 2020-06-19 2020-10-30 江苏益帆高分子材料有限公司 Antibacterial LDPE produced by grafting reaction extrusion and preparation process thereof
CN111909481A (en) * 2020-07-20 2020-11-10 江苏宝安电缆有限公司 Antibacterial LDPE produced by grafting reactive extrusion and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113234298A (en) * 2021-06-10 2021-08-10 江苏宝源高新电工有限公司 High-performance LDPE ionic polymer and preparation method thereof
CN113667258A (en) * 2021-08-24 2021-11-19 江苏宝安电缆有限公司 High-strength super-toughness HDPE polymer and preparation method thereof

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