CN114716792B - PET composite material with low odor and good physical properties and preparation method thereof - Google Patents
PET composite material with low odor and good physical properties and preparation method thereof Download PDFInfo
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- CN114716792B CN114716792B CN202110012844.8A CN202110012844A CN114716792B CN 114716792 B CN114716792 B CN 114716792B CN 202110012844 A CN202110012844 A CN 202110012844A CN 114716792 B CN114716792 B CN 114716792B
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000000704 physical effect Effects 0.000 title claims abstract description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 56
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 56
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 22
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 21
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 11
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a low-odor polyethylene terephthalate (PET) composite material with good physical properties, which is prepared from the following components in parts by weight: 80-100 parts of PET, 8-12 parts of modifier polyglycidyl methacrylate-styrene-dimethylsiloxane and 0.1-0.5 part of antioxidant. The invention also discloses a preparation method of the PET composite material. The modifier P (GMA-St-DMS) in the PET composite material prepared by the invention can well improve the physical properties of the PET material; the supercritical carbon dioxide is introduced into the PET composite material, and the volatile small molecules in the fluid are adsorbed through the strong permeation and dissolution capacity of the supercritical carbon dioxide, so that the odor of the PET composite material is improved. The PET composite material prepared by the invention has excellent application prospect in the field of automobile materials.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a PET composite material with low odor and good physical properties and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is a widely applied high polymer polyester resin, and has the advantages of good fatigue resistance, good heat resistance, good dimensional stability and the like, but in some specific automobile material fields, the requirements on the odor and physical properties of PET are high, and the common PET material cannot meet the requirements, so that the application of the PET composite material in some automobile material fields is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a PET composite material with low odor and good physical properties and a preparation method thereof.
The aim of the invention is realized by the following technical scheme:
a PET composite material with low odor and good physical properties is prepared from the following components in parts by weight:
80-100 parts of PET (polyethylene terephthalate),
8-12 parts of modifier poly glycidyl methacrylate-styrene-dimethyl siloxane,
0.1-0.5 part of antioxidant.
As a preferred technical scheme, the modifier is polyglycidyl methacrylate-styrene-dimethylsiloxane, which is called as modifier P (GMA-St-DMS) for short, and the preparation steps are as follows:
(1) Adding emulsifier sodium dodecyl benzene sulfonate, initiator sodium persulfate, glycidyl methacrylate, styrene, crosslinking agent ethylene glycol dimethacrylate and deionized water into a reaction vessel, and stirring at 60-80 ℃ for reaction for 10-16h to obtain a solution A; further preferably, the mass ratio of the emulsifier sodium dodecyl benzene sulfonate, the initiator sodium persulfate, the glycidyl methacrylate, the styrene, the crosslinking agent ethylene glycol dimethacrylate and the deionized water is (0.2-0.4): (0.1-0.3): (30-40): (20-30): (0.1-0.3): (160-200).
(2) Weighing a solution A, an initiator sodium persulfate and dimethyl dichlorosilane, adding the solution A, the initiator sodium persulfate and the dimethyl dichlorosilane into a reaction vessel, and stirring the reaction vessel at 70-90 ℃ for 8-12 hours to obtain a solution B, wherein the mass ratio of the solution A to the initiator sodium persulfate to the dimethyl dichlorosilane is (60-80): (0.1-0.3): (10-16).
(3) Weighing a solution B and a magnesium sulfate solution, adding the solution B and the magnesium sulfate solution into a reaction vessel, and stirring and reacting for 6-8 hours at 50-70 ℃ to obtain a solution C; further preferably, the mass ratio of the solution B to the magnesium sulfate solution is (70-90): (20-30).
(4) And (3) carrying out suction filtration, washing and drying on the solution C to obtain the modifier P (GMA-St-DMS).
As a preferable technical scheme, the antioxidant is at least one of an antioxidant 168, an antioxidant 1010 and an antioxidant 1330.
The invention also provides a preparation method of the PET composite material, which comprises the following steps:
(1) Weighing PET, a modifier P (GMA-St-DMS) and an antioxidant according to a proportion, putting the materials into an autoclave in a supercritical carbon dioxide environment, and uniformly mixing to obtain a mixture;
(2) And (3) adding the mixture obtained in the step (1) into a double-screw extruder for extrusion granulation, and obtaining the PET composite material.
Preferably, the autoclave is at a temperature of 30-40℃and a pressure of 6-8MPa.
Further preferably, the twin-screw extruder comprises six temperature zones which are arranged in sequence, and the temperatures of the zones are respectively: the temperature of the first area is 240-260 ℃, the temperature of the second area is 280-300 ℃, the temperature of the third area is 280-300 ℃, the temperature of the fourth area is 280-300 ℃, the temperature of the fifth area is 280-300 ℃, the temperature of the sixth area is 280-300 ℃, the temperature of the machine head is 280-300 ℃, and the rotating speed of the screw is 200-280 r/min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention prepares a novel modifier P (GMA-St-DMS) which can well improve the physical properties of PET materials, and has important significance.
(2) The invention introduces supercritical carbon dioxide, and adsorbs volatile micromolecules in PET through the strong permeation and dissolution capacity, so that the odor of the PET composite material is improved, and the invention has important significance.
Detailed Description
The invention will be further illustrated with reference to examples. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The types and suppliers of reagents used in the examples and comparative examples below are provided solely to illustrate the sources and compositions of reagents used in the experiments of the invention and are well disclosed and do not represent the inability to practice the invention using other reagents of the same type or provided by other suppliers.
The raw materials used in the following examples are as follows:
PET (model 008L), aclo, canada; sodium dodecyl benzene sulfonate, jinan Miantian chemical Co., ltd; sodium persulfate, guangzhou chemical Co., ltd; styrene, jinan Ming Xin chemical Co., ltd; glycidyl methacrylate, nanjing Rong chemical engineering Co., ltd; ethylene glycol dimethacrylate, shandong Yukang chemical Co., ltd; dimethyl dichlorosilane, hubei Yongku technology Co., ltd; deionized water, shanghai pure water treatment technologies limited; antioxidant 168, antioxidant 1010, antioxidant 1330, basf company.
Preparation example 1
(1) 2g of emulsifier sodium dodecyl benzene sulfonate, 1g of initiator sodium persulfate, 300g of glycidyl methacrylate, 200g of styrene, 1g of crosslinking agent ethylene glycol dimethacrylate and 1.6kg of deionized water are weighed, added into a reaction vessel, and stirred and reacted for 10 hours at 60 ℃ to obtain a solution A.
(2) 600g of solution A, 1g of initiator sodium persulfate and 100g of dimethyl dichlorosilane are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 8 hours at 70 ℃ to obtain solution B.
(3) 700g of solution B and 200g of magnesium sulfate solution are weighed, added into a reaction vessel, and stirred and reacted for 6 hours at 50 ℃ to obtain solution C.
(4) And (3) carrying out suction filtration, washing and drying on the solution C to obtain the modifier P (GMA-St-DMS) X1.
Example 1
(1) 80 parts of PET, 8 parts of modifier P (GMA-St-DMS) X1 and 0.1 part of Irganox1010 are weighed and put into an autoclave in a supercritical carbon dioxide environment to be uniformly mixed to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material P1.
Wherein the temperature of the autoclave is 30 ℃, the pressure is 6MPa, and the temperature of each area of the double-screw extruder and the screw rotating speed are respectively: the temperature of the first area is 240 ℃, the temperature of the second area is 280 ℃, the temperature of the third area is 280 ℃, the temperature of the fourth area is 280 ℃, the temperature of the fifth area is 280 ℃, the temperature of the sixth area is 280 ℃, the temperature of the machine head is 280 ℃, and the rotating speed of the screw is 200r/min.
Preparation example 2
(1) 4g of emulsifier sodium dodecyl benzene sulfonate, 3g of initiator sodium persulfate, 400g of glycidyl methacrylate, 300g of styrene, 3g of crosslinking agent ethylene glycol dimethacrylate and 2.0kg of deionized water are weighed, added into a reaction vessel, and stirred and reacted for 16 hours at 80 ℃ to obtain a solution A.
(2) 800g of solution A, 3g of initiator sodium persulfate and 160g of dimethyl dichlorosilane are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 12 hours at 90 ℃ to obtain solution B.
(3) 900g of solution B and 300g of magnesium sulfate solution are weighed, added into a reaction vessel and stirred at 70 ℃ for reaction for 8 hours, thus obtaining solution C.
(4) And (3) carrying out suction filtration, washing and drying on the solution C to obtain the modifier P (GMA-St-DMS) X2.
Example 2
(1) Weighing 100 parts of PET, 12 parts of modifier P (GMA-St-DMS) X2, 0.1 part of Irganox1010, 0.2 part of Irganox168 and 0.2 part of Irganox1330, putting into an autoclave in a supercritical carbon dioxide environment, and uniformly mixing to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material P2.
Wherein the temperature of the autoclave is 40 ℃, the pressure is 8MPa, and the temperature of each area of the double-screw extruder and the screw rotating speed are respectively: the temperature of the first area is 260 ℃, the temperature of the second area is 300 ℃, the temperature of the third area is 300 ℃, the temperature of the fourth area is 300 ℃, the temperature of the fifth area is 300 ℃, the temperature of the sixth area is 300 ℃, the temperature of the machine head is 300 ℃, and the rotating speed of the screw is 280r/min.
Preparation example 3
(1) 3g of emulsifier sodium dodecyl benzene sulfonate, 2g of initiator sodium persulfate, 350g of glycidyl methacrylate, 250g of styrene, 2g of crosslinking agent ethylene glycol dimethacrylate and 1.8kg of deionized water are weighed, added into a reaction vessel, and stirred and reacted for 13 hours at 70 ℃ to obtain a solution A.
(2) 700g of solution A, 2g of initiator sodium persulfate and 130g of dimethyl dichlorosilane are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 10 hours at 80 ℃ to obtain solution B.
(3) 800g of solution B and 250g of magnesium sulfate solution are weighed, added into a reaction vessel and stirred at 60 ℃ for reaction for 7 hours, thus obtaining solution C.
(4) And (3) carrying out suction filtration, washing and drying on the solution C to obtain the modifier P (GMA-St-DMS) X3.
Example 3
(1) 90 parts of PET, 10 parts of modifier P (GMA-St-DMS) X3, 0.1 part of Irganox168 and 0.2 part of Irganox1010 are weighed and put into an autoclave in a supercritical carbon dioxide environment to be uniformly mixed to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material P3.
Wherein the temperature of the autoclave is 35 ℃, the pressure is 7MPa, and the temperature of each area of the double-screw extruder and the screw rotating speed are respectively: the temperature of the first area is 250 ℃, the temperature of the second area is 290 ℃, the temperature of the third area is 290 ℃, the temperature of the fourth area is 290 ℃, the temperature of the fifth area is 290 ℃, the temperature of the sixth area is 290 ℃, the temperature of the machine head is 290 ℃, and the rotating speed of the screw is 240r/min.
Preparation example 4
(1) 2g of emulsifier sodium dodecyl benzene sulfonate, 3g of initiator sodium persulfate, 380g of glycidyl methacrylate, 220g of styrene, 1g of crosslinking agent ethylene glycol dimethacrylate and 1.9kg of deionized water are weighed, added into a reaction vessel, and stirred and reacted for 11 hours at 65 ℃ to obtain a solution A.
(2) 710g of solution A, 3g of initiator sodium persulfate and 120g of dimethyl dichlorosilane are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 11 hours at 75 ℃ to obtain solution B.
(3) 780g of solution B and 210g of magnesium sulfate solution are weighed, added into a reaction vessel and stirred at 55 ℃ for reaction for 7 hours to obtain solution C.
(4) And (3) carrying out suction filtration, washing and drying on the solution C to obtain the modifier P (GMA-St-DMS) X4.
Example 4
(1) Weighing 85 parts of PET, 9 parts of modifier P (GMA-St-DMS) X4, 16 parts of supercritical carbon dioxide, 0.1 part of Irganox1010 and 0.2 part of Irganox1330, putting into an autoclave in a supercritical carbon dioxide environment, and uniformly mixing to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material P4.
Wherein the temperature of the autoclave is 40 ℃, the pressure is 6MPa, and the temperature of each area of the double-screw extruder and the screw rotating speed are respectively: the temperature of the first zone is 245 ℃, the temperature of the second zone is 285 ℃, the temperature of the third zone is 285 ℃, the temperature of the fourth zone is 285 ℃, the temperature of the fifth zone is 285 ℃, the temperature of the sixth zone is 285 ℃, the temperature of the machine head is 285 ℃, and the rotating speed of the screw is 255r/min.
Preparation example 5
(1) 3g of emulsifier sodium dodecyl benzene sulfonate, 3g of initiator sodium persulfate, 380g of glycidyl methacrylate, 210g of styrene, 1g of crosslinking agent ethylene glycol dimethacrylate and 1.9kg of deionized water are weighed, added into a reaction vessel, and stirred and reacted for 14 hours at 65 ℃ to obtain a solution A.
(2) 690g of solution A, 2g of initiator sodium persulfate and 140g of dimethyl dichlorosilane are weighed and added into a reaction vessel, and the mixture is stirred and reacted for 11 hours at 75 ℃ to obtain solution B.
(3) 780g of solution B and 240g of magnesium sulfate solution are weighed, added into a reaction vessel and stirred at 55 ℃ for reaction for 8 hours to obtain solution C.
(4) And (3) carrying out suction filtration, washing and drying on the solution C to obtain the modifier P (GMA-St-DMS) X5.
Example 5
(1) Weighing 95 parts of PET, 11 parts of modifier P (GMA-St-DMS) X5, 0.1 part of Irganox1010 and 0.1 part of Irganox168, putting into an autoclave in a supercritical carbon dioxide environment, and uniformly mixing to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material P5.
Wherein the temperature of the autoclave is 35 ℃, the pressure is 7MPa, and the temperature of each area of the double-screw extruder and the screw rotating speed are respectively: the temperature of the first area is 250 ℃, the temperature of the second area is 295 ℃, the temperature of the third area is 295 ℃, the temperature of the fourth area is 295 ℃, the temperature of the fifth area is 295 ℃, the temperature of the sixth area is 295 ℃, the temperature of the machine head is 295 ℃, and the rotating speed of the screw is 270r/min.
Comparative example 1
(1) Weighing 100 parts of PET, 0.1 part of Irganox1010 and 0.2 part of Irganox168, mixing and stirring uniformly to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material D1.
Wherein the temperature and the screw rotating speed of each zone of the double-screw extruder are respectively as follows: the temperature of the first area is 250 ℃, the temperature of the second area is 295 ℃, the temperature of the third area is 295 ℃, the temperature of the fourth area is 295 ℃, the temperature of the fifth area is 295 ℃, the temperature of the sixth area is 295 ℃, the temperature of the machine head is 295 ℃, and the rotating speed of the screw is 270r/min.
Comparative example 2
(1) Weighing 80 parts of PET and 0.1 part of Irganox1010, putting into an autoclave in a supercritical carbon dioxide environment, and uniformly mixing to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material D2.
Wherein the temperature of the autoclave is 30 ℃, the pressure is 6MPa, and the temperature of each area of the double-screw extruder and the screw rotating speed are respectively: the temperature of the first area is 240 ℃, the temperature of the second area is 280 ℃, the temperature of the third area is 280 ℃, the temperature of the fourth area is 280 ℃, the temperature of the fifth area is 280 ℃, the temperature of the sixth area is 280 ℃, the temperature of the machine head is 280 ℃, and the rotating speed of the screw is 200r/min.
Comparative example 3
(1) 80 parts of PET, 8 parts of modifier P (GMA-St-DMS) X1 and 0.1 part of Irganox1010 are weighed and put into an autoclave for uniform mixing to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PET composite material D3.
Wherein the temperature of the autoclave is 30 ℃, the pressure is 6MPa, and the temperature of each area of the double-screw extruder and the screw rotating speed are respectively: the temperature of the first area is 240 ℃, the temperature of the second area is 280 ℃, the temperature of the third area is 280 ℃, the temperature of the fourth area is 280 ℃, the temperature of the fifth area is 280 ℃, the temperature of the sixth area is 280 ℃, the temperature of the machine head is 280 ℃, and the rotating speed of the screw is 200r/min.
The PET composites prepared in examples 1-5 and comparative examples 1-3 were subjected to performance testing by using an injection molding machine to prepare sample bars, and the test data are shown in Table 1 below:
TABLE 1 Performance test results
Note that: in Table 1, the spline model and correlation conditions used for the correlation test are as follows:
the model of the stretching spline is (170.0+/-5.0) mm (13.0+/-0.5) mm (3.2+/-0.2) mm, and the stretching speed is 50mm/min; the type of the cantilever beam notch impact strength spline is as follows: (125.0+ -5.0) mm (13.0+ -0.5) mm (3.2+ -0.2) mm, notch machined, notch depth (2.6+ -0.2) mm. The odor detection standard employs VDA270, divided into 6 classes: 1 = odorless; 2 = slightly odorous; 3 = tasty, but not irritating; 4 = having a pungent odor; 5 = strong pungent odor; 6 = intolerable taste, test procedure 30g of sample were placed in a 1L container, covered with a lid seal, and placed in a high temperature oven at 40 ℃ for 24h.
As can be seen from Table 1 above, examples 1-5 were better in physical properties and odor properties than comparative example 1, examples 1-5 were better in physical properties than comparative example 2, and examples 1-5 were better in odor properties than comparative example 3. This demonstrates that the PET composite material of this patent is excellent in physical properties and good in odor. This greatly expands the application field of PET composite materials, and has very important significance.
The present invention is not limited to the embodiments described, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present invention, and are intended to be included in the scope of the present invention as defined in the appended claims.
Claims (5)
1. A PET composite material having good low odor physical properties, characterized by: the composition is prepared from the following components in parts by weight:
80-100 parts of PET (polyethylene terephthalate),
8-12 parts of modifier poly glycidyl methacrylate-styrene-dimethyl siloxane,
0.1-0.5 part of antioxidant;
the preparation method of the modifier, namely the polyglycidyl methacrylate-styrene-dimethylsiloxane comprises the following steps:
(1) Adding emulsifier sodium dodecyl benzene sulfonate, initiator sodium persulfate, glycidyl methacrylate, styrene, crosslinking agent ethylene glycol dimethacrylate and deionized water into a reaction vessel, and stirring at 60-80 ℃ for reaction for 10-16h to obtain a solution A; the mass ratio of the emulsifier sodium dodecyl benzene sulfonate, the initiator sodium persulfate, the glycidyl methacrylate, the styrene, the crosslinking agent ethylene glycol dimethacrylate and the deionized water is (0.2-0.4): (0.1-0.3): (30-40): (20-30): (0.1-0.3): (160-200);
(2) Weighing the solution A, an initiator sodium persulfate and dimethyl dichlorosilane, adding the solution A and the initiator sodium persulfate and the dimethyl dichlorosilane into a reaction vessel, and stirring and reacting at 70-90 ℃ for 8-12h to obtain a solution B; the mass ratio of the solution A to the initiator sodium persulfate to the dimethyl dichlorosilane is (60-80): (0.1-0.3): (10-16);
(3) Weighing a solution B and a magnesium sulfate solution, adding the solution B and the magnesium sulfate solution into a reaction vessel, and stirring and reacting for 6-8 hours at 50-70 ℃ to obtain a solution C; the mass ratio of the solution B to the magnesium sulfate solution is (70-90): (20-30);
(4) Carrying out suction filtration, washing and drying on the solution C to obtain a modifier, namely polyglycidyl methacrylate-styrene-dimethylsiloxane;
the preparation method of the PET composite material comprises the following steps:
(1) Weighing PET, modifier polyglycidyl methacrylate-styrene-dimethyl siloxane and antioxidant according to a proportion, putting into an autoclave in a supercritical carbon dioxide environment, and uniformly mixing to obtain a mixture;
(2) And (3) adding the mixture obtained in the step (1) into a double-screw extruder for extrusion granulation, and obtaining the PET composite material.
2. The PET composite of claim 1, wherein: the antioxidant is at least one of antioxidant 168, antioxidant 1010 and antioxidant 1330.
3. A process for the preparation of a PET composite material according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) Weighing PET, modifier polyglycidyl methacrylate-styrene-dimethyl siloxane and antioxidant according to a proportion, putting into an autoclave in a supercritical carbon dioxide environment, and uniformly mixing to obtain a mixture;
(2) And (3) adding the mixture obtained in the step (1) into a double-screw extruder for extrusion granulation, and obtaining the PET composite material.
4. A method of preparation according to claim 3, characterized in that: the temperature of the autoclave in the step (1) is 30-40 ℃ and the pressure is 6-8MPa.
5. A method of preparation according to claim 3, characterized in that: in the step (2), the twin-screw extruder comprises six temperature areas which are sequentially arranged, and the temperatures of the areas are respectively: the temperature of the first area is 240-260 ℃, the temperature of the second area is 280-300 ℃, the temperature of the third area is 280-300 ℃, the temperature of the fourth area is 280-300 ℃, the temperature of the fifth area is 280-300 ℃, the temperature of the sixth area is 280-300 ℃, the temperature of the machine head is 280-300 ℃, and the rotating speed of the screw is 200-280 r/min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102837408A (en) * | 2012-09-18 | 2012-12-26 | 贵州凯科特材料有限公司 | Double screw extruder and method for using same to prepare light-smell polypropylene |
| CN103819604A (en) * | 2014-03-11 | 2014-05-28 | 合肥工业大学 | Toughening agent with chain extension function and application of toughening agent in engineering plastic processing |
| CN107090128A (en) * | 2017-05-13 | 2017-08-25 | 合肥会通新材料有限公司 | It is a kind of to prepare overcritical low smell, the low method for distributing polypropylene material |
| CN108727660A (en) * | 2017-04-20 | 2018-11-02 | 中国石化扬子石油化工有限公司 | A kind of preparation method of low smell polyethylene composition |
| CN109081925A (en) * | 2018-07-02 | 2018-12-25 | 苏州旭光聚合物有限公司 | A kind of supercritical fluid green method efficiently removing smell and VOCs in plastics simultaneously |
| CN111253611A (en) * | 2020-03-19 | 2020-06-09 | 上海越科新材料股份有限公司 | PET foaming method |
-
2021
- 2021-01-06 CN CN202110012844.8A patent/CN114716792B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102837408A (en) * | 2012-09-18 | 2012-12-26 | 贵州凯科特材料有限公司 | Double screw extruder and method for using same to prepare light-smell polypropylene |
| CN103819604A (en) * | 2014-03-11 | 2014-05-28 | 合肥工业大学 | Toughening agent with chain extension function and application of toughening agent in engineering plastic processing |
| CN108727660A (en) * | 2017-04-20 | 2018-11-02 | 中国石化扬子石油化工有限公司 | A kind of preparation method of low smell polyethylene composition |
| CN107090128A (en) * | 2017-05-13 | 2017-08-25 | 合肥会通新材料有限公司 | It is a kind of to prepare overcritical low smell, the low method for distributing polypropylene material |
| CN109081925A (en) * | 2018-07-02 | 2018-12-25 | 苏州旭光聚合物有限公司 | A kind of supercritical fluid green method efficiently removing smell and VOCs in plastics simultaneously |
| CN111253611A (en) * | 2020-03-19 | 2020-06-09 | 上海越科新材料股份有限公司 | PET foaming method |
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