CN107057298A - A kind of fire-retardant degradable low melting point polyester chip and preparation method thereof - Google Patents
A kind of fire-retardant degradable low melting point polyester chip and preparation method thereof Download PDFInfo
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- CN107057298A CN107057298A CN201710220407.9A CN201710220407A CN107057298A CN 107057298 A CN107057298 A CN 107057298A CN 201710220407 A CN201710220407 A CN 201710220407A CN 107057298 A CN107057298 A CN 107057298A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 94
- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 238000002844 melting Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000008018 melting Effects 0.000 title claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 103
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 73
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 41
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005886 esterification reaction Methods 0.000 claims abstract description 24
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 23
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 15
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 15
- -1 polyethylene Polymers 0.000 claims abstract description 15
- 239000004698 Polyethylene Substances 0.000 claims abstract description 14
- 229920000573 polyethylene Polymers 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 56
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052787 antimony Inorganic materials 0.000 abstract 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 1
- 238000009264 composting Methods 0.000 abstract 1
- 239000013585 weight reducing agent Substances 0.000 abstract 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 241000272517 Anseriformes Species 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004753 textile Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides fire-retardant degradable low melting point polyester chip of one kind and preparation method thereof, described fire-retardant degradable low melting point polyester chip is blended by the raw material of following mass percent to be made：Fire retardant 8%~12%, low melting point polyester chip 88%~92%；Described fire retardant is blended by nanometric magnesium hydroxide, nanometer grade antimony trioxide, coupling agent maleated polyethylene wax graft and is made；Described low melting point polyester chip is obtained by p-phthalic acid, ethylene glycol, diglycol, antimony glycol through esterification, polycondensation reaction；The measure of anti-flammability is carried out to product of the present invention, limited oxygen index reaches 28.2~30.1%, and conventional PET limited oxygen index is only 21%；Batten is placed to the measure that molecular weight is carried out after a period of time under ultraviolet light or composting conditionses, increased over time, molecular weight reduction is faster, illustrates that batten has been degraded.
Description
(I) technical field
The invention relates to the field of low-melting-point polyester modification, in particular to a novel flame-retardant degradable low-melting-point polyester chip and a preparation method thereof.
(II) background of the invention
The low-melting-point polyester is generally a modified copolyester with a melting point of 100-210 ℃, and usually, in the conventional polyester polymerization process, a modified component is added to destroy the regularity of a molecular chain and change the rigid structure of a polyester molecule, so that the purpose of reducing the melting point is achieved. The low-melting point polyester has the advantages of good fluidity, low melting point, good compatibility with the conventional polyester on the premise of keeping partial characteristics of the conventional polyester and the like, and is widely applied to the industries of polyester color master batches, non-woven fabrics, textiles and the like. In recent years, many researches on low-melting point polyesters are reported, and the reported preparation methods of the low-melting point polyesters are that components such as dibasic acid, dihydric alcohol and the like are added in the conventional polyester production process, so that the modified components are mixed with PTA and EG to react and copolymerize. Common diacids include aliphatic diacids and aromatic diacids, such as isophthalic acid, phthalic acid, adipic acid, and the like, and diols such as butanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, polyethylene glycol, and the like. In the academic paper, synthesis and performance research of low-melting point polyester, Tangshi et al, in the text of the study, isophthalic acid and adipic acid are added into PTA and EG to react to prepare low-melting point polyester, and the change relationship between polycondensation time and crystallization rate of the low-melting point polyester along with the addition amount of a modification component is researched. 2006 synthesis and performance research of low-melting point polyester discloses that a third monomer containing a dihydroxy end group and a butanediol fourth monomer are introduced into a conventional polyester molecular structure, and the melting point of the synthesized low-melting point polyester reaches below 130 ℃. Low-melting point polyester having a melting point of 110 ℃ was obtained by substituting isophthalic acid, adipic acid and neopentyl glycol for a part of PTA and EG by Endoconman et al in the text "development and analysis of Low-melting point polyester". In 2011, synthesis and application research of low-melting-point polyester, isopropanol, adipic acid and diethylene glycol are used by queen geese to replace part of purified terephthalic acid and ethylene glycol, and the melting point of the obtained low-melting-point polyester is 110 ℃. However, the current preparation method modifies the low-melting point polyester simply in order to prepare the low-melting point polyester with the melting point lower than that of the conventional polyester, and particularly, the research on the obtained flame-retardant and degradable low-melting point polyester is few, the effect is not ideal, and the conventional low-melting point polyester chip still cannot meet the requirements of people.
The invention adopts the methods of mixing esterification and melt blending to prepare the flame-retardant degradable low-melting-point polyester chip, so that the magnesium hydroxide and antimony trioxide mixed flame retardant subjected to surface treatment are uniformly dispersed in the low-melting-point polyester, and the low-melting-point polyester chip is endowed with good flame-retardant property. The maleic anhydride polyethylene wax graft (PEW-g-MAH) as the surface treating agent contains active groups and can be degraded under the conditions of illumination, compost and the like, and the addition of the PEW-g-MAH ensures that the low-melting polyester chip is more easily degraded. Compared with the conventional polyester, the flame-retardant degradable low-melting-point polyester chip prepared by the method has good flame retardance and improved degradability, and the method has relatively simple process and is suitable for large-scale industrial production.
Disclosure of the invention
The invention aims to provide a low-melting-point polyester chip with the characteristics of small addition amount, low cost, simple preparation method, low melting point, flame retardance and degradability and a preparation method thereof.
The invention adopts the following technical scheme:
the flame-retardant degradable low-melting-point polyester chip is prepared by blending the following raw materials in percentage by mass:
8 to 12 percent of fire retardant
88 to 92 percent of low-melting-point polyester chip
Wherein,
the flame retardant is prepared by blending the following components in percentage by mass:
44-55% of nano-scale magnesium hydroxide, 43-54% of nano-scale antimony trioxide and 1-2% of coupling agent, wherein the coupling agent comprises the following components in percentage by weight: maleic anhydride polyethylene wax grafts (PEW-g-MAH);
the low-melting-point polyester chip is obtained by esterification and polycondensation reaction of the following components:
pure Terephthalic Acid (PTA), Ethylene Glycol (EG), diethylene glycol (glycol modifier) and ethylene glycol antimony (catalyst);
based on the total mass of PTA and EG, the mass percent of PTA is 60-65%, and the mass percent of EG is 35-40%;
the mass usage of the diethylene glycol is 10-20% of the mass of EG;
the mass consumption of the ethylene glycol antimony is 0.1-0.2% of the mass of the PTA.
The invention also provides a preparation method of the flame-retardant degradable low-melting-point polyester chip, which comprises the following steps:
(1) preparation of Low melting polyester chips
Weighing PTA, EG, diethylene glycol and ethylene glycol antimony according to a formula proportion, adding the PTA, EG, diethylene glycol and ethylene glycol antimony into a polymerization reaction kettle (such as a GSH-5 type 5L polymerization reaction kettle, Winhalay rain chemical equipment Limited company), starting a stirring motor (Shandong Zibobosan Subo micromotor Limited company, model 130SZ02A1), carrying out esterification reaction under the conditions of 0.2-0.3 MPa of pressure and 250-260 ℃ of temperature, finishing the esterification reaction when the theoretical water yield reaches more than 95%, then carrying out polycondensation reaction for 1-1.5 h under the conditions of 250-300 Pa of vacuum degree and 265-270 ℃ of temperature, and then continuing the polycondensation reaction for 2.5-3 h under the conditions of 30-50 Pa of vacuum degree and 275-280 ℃; when the power value of the stirring motor reaches 75-78W, discharging, cooling, granulating and drying to obtain the low-melting-point polyester chip;
the theoretical water yield is calculated according to the actual feeding amount of reactants and the mass conservation principle in the acid-base neutralization reaction, and the method for judging the end of the esterification reaction is a conventional technical means known in the field;
(2) preparation of flame retardant
Weighing nanoscale magnesium hydroxide and nanoscale antimony trioxide according to a formula ratio, mixing in a high-speed kneader (MHZ-5L electric heating vacuum kneader manufactured by Nanhai Jinchuntai mechanical equipment Co., Ltd., Fushan City) for 5-10 min, adding a maleic anhydride polyethylene wax graft serving as a coupling agent, continuously mixing for 15-20 min, and discharging to obtain the flame retardant;
the parameters of the high-speed kneader are set as follows: the temperature is 130-170 ℃, and the speed is 28-42 rpm/min;
(3) adding the low-melting-point polyester chip prepared in the step (1) and the flame retardant prepared in the step (2) into a double-screw extruder according to a formula ratio for extrusion, and then cooling, granulating and drying to obtain the flame-retardant degradable low-melting-point polyester chip;
the parameters of the double-screw extruder (Nanjing Kelida mechanical equipment Co., Ltd., TSE65 type co-rotating double-screw extruder) are set as follows: the temperatures of the heating zones were as follows: the temperature of the first zone is 150-160 ℃, the temperature of the second zone is 160-165 ℃, the temperature of the third zone is 165-168 ℃, the temperature of the fourth zone is 165-168 ℃, the temperature of the fifth zone is 168-172 ℃, the temperature of the sixth zone is 168-165 ℃, the rotating speed of a main engine is 200-300 r/min, the aperture of a filter screen is 30-60 mu m, and the pressure is 10-12 MPa.
Compared with the prior art, the invention has the beneficial effects that: the flame-retardant degradable low-melting-point polyester chip prepared by the invention has the advantages that the melting point is reduced to 145-155 ℃ due to the damage to the rigid structure and the regularity of polyethylene terephthalate (PET) molecules; the low-melting-point polyester matrix contains a mixed flame retardant of magnesium hydroxide and antimony trioxide, so that the flame retardant effect is obviously improved; the maleic anhydride polyethylene wax graft not only serves as a surface treatment agent of the mixed flame retardant, but also is introduced into the low-melting-point polyester molecule due to the degradable active group contained in the molecular structure, so that the degradation of the low-melting-point polyester is promoted. The flame retardance of the obtained slices is measured, the limited oxygen index reaches 28.2-30.1%, and the limited oxygen index of the conventional PET fiber is only 21%; the molecular weight is measured after the bars have been left for a period of time under UV light or compost conditions, and the molecular weight decreases more rapidly with time, indicating that the bars have degraded.
(IV) detailed description of the preferred embodiments
The technical solutions of the present invention are further described below with reference to specific examples, but the scope of the present invention is not limited thereto.
The maleic anhydride polyethylene wax graft (PEW-g-MAH) used in the following examples had a grafting ratio of 2%, which was provided by Hangzhou Hai-Polymer materials Co.
Example 1
The flame-retardant degradable low-melting-point polyester chip comprises the following raw materials:
0.22kg of flame retardant and 2.53kg of low-melting-point polyester chips;
wherein, the flame retardant is prepared by blending the following components:
0.10kg of nano-magnesium hydroxide, 0.12kg of nano-antimony trioxide and 4.40g of maleic anhydride polyethylene wax graft serving as a coupling agent;
the low-melting-point polyester chip is obtained by esterification and polycondensation reaction of the following components:
PTA 2.01kg, EG 1.2L, diethylene glycol 0.134kg, ethylene glycol antimony 2.01 g.
The preparation method comprises the following steps:
(1) preparation of Low melting polyester chips
Weighing PTA, EG, diethylene glycol and ethylene glycol antimony according to a formula proportion, adding the PTA, EG, diethylene glycol and ethylene glycol antimony into a 5L polymerization reaction kettle (GSH-5 type 5L polymerization reaction kettle, Winhai rain chemical equipment Co., Ltd.), starting a stirring motor (Shandong Zibobos Subo micromotor Co., Ltd., model No. 130SZ02A1), carrying out esterification reaction under the pressure of 0.3MPa and the temperature of 260 ℃, calculating out 390ml of theoretical water yield according to the acid-base neutralization reaction quality conservation principle, finishing the esterification reaction when the distilled water amount reaches about 370ml, then carrying out polycondensation reaction for 1h under the conditions of vacuum degree of 300Pa and temperature of 268 ℃, and then gradually switching to the conditions of vacuum degree of 30Pa and temperature of 280 ℃ to continue the polycondensation reaction for 3 h; when the power value of the stirring motor reaches 78W, discharging, cooling, granulating and drying to obtain the low-melting-point polyester chip;
(2) preparation of flame retardant
Weighing nanoscale magnesium hydroxide and nanoscale antimony trioxide according to a formula ratio, mixing in a high-speed kneader (MHZ-5L electric heating vacuum kneader manufactured by Nanhai Jinchuntai mechanical equipment Co., Ltd., Fushan City) for 5min, adding a maleic anhydride polyethylene wax graft serving as a coupling agent, continuously mixing for 15min, and discharging to obtain the flame retardant;
the parameters of the high-speed kneader are set as follows: the temperature is 150 ℃, and the speed is 1500 rpm/min;
(3) adding the low-melting-point polyester chip prepared in the step (1) and the flame retardant prepared in the step (2) into a double-screw extruder (TSE 65 type co-rotating double-screw extruder, Nanjing Kelida mechanical equipment Co., Ltd.) according to a formula ratio, extruding, cooling, granulating and drying to obtain the flame-retardant degradable low-melting-point polyester chip;
the parameters of the double-screw extruder are as follows: the six heating zones have the temperature of 150 ℃, 160 ℃, 165 ℃, 168 ℃ and 165 ℃, the rotating speed of a main machine of 200r/min, the aperture of a filter screen of 30 mu m and the pressure of 10 MPa.
Preparing the obtained slices into strip samples in a molten state, and measuring the limiting oxygen index to be 30.1%; the degradation performance is also greatly improved.
Example 2
The flame-retardant degradable low-melting-point polyester chip comprises the following raw materials:
0.25kg of flame retardant and 2.55kg of low-melting-point polyester chips;
wherein, the flame retardant is prepared by blending the following components:
0.14kg of nano-magnesium hydroxide, 0.11kg of nano-antimony trioxide and 2.50g of maleic anhydride polyethylene wax graft serving as a coupling agent;
the low-melting-point polyester chip is obtained by esterification and polycondensation reaction of the following components:
PTA 1.89kg, EG 1.04L, diethylene glycol 0.17kg, ethylene glycol antimony 3.78 g.
The preparation method comprises the following steps:
(1) preparation of Low melting polyester chips
Weighing PTA, EG, diethylene glycol and ethylene glycol antimony according to a formula proportion, adding the PTA, EG, diethylene glycol and ethylene glycol antimony into a 5L polymerization reaction kettle (GSH-5 type 5L polymerization reaction kettle, Winhai rain chemical equipment Co., Ltd.), starting a stirring motor (Shandong Zibobos Subo micromotor Co., Ltd., model No. 130SZ02A1), carrying out esterification reaction under the pressure of 0.3MPa and the temperature of 260 ℃, calculating to obtain the theoretical water yield of 337ml according to the acid-base neutralization reaction mass conservation principle, finishing the esterification reaction when the distilled water amount reaches about 320ml, then carrying out polycondensation reaction for 1h under the conditions of vacuum degree of 280Pa and temperature of 270 ℃, and then gradually switching to the conditions of vacuum degree of 50Pa and temperature of 275 ℃ to continue the polycondensation reaction for 2.5 h; when the power value of the stirring motor reaches 75W, discharging, cooling, granulating and drying to obtain the low-melting-point polyester chip;
(2) preparation of flame retardant
Weighing nanoscale magnesium hydroxide and nanoscale antimony trioxide according to a formula ratio, mixing in a high-speed kneader (MHZ-5L electric heating vacuum kneader manufactured by Nanhai Jinchuntai mechanical equipment Co., Ltd., Fushan City) for 10min, adding a maleic anhydride polyethylene wax graft serving as a coupling agent, continuously mixing for 20min, and discharging to obtain the flame retardant;
the parameters of the high-speed kneader are set as follows: the temperature is 150 ℃, and the speed is 1500 rpm/min;
(3) adding the low-melting-point polyester chip prepared in the step (1) and the flame retardant prepared in the step (2) into a double-screw extruder (TSE 65 type co-rotating double-screw extruder, Nanjing Kelida mechanical equipment Co., Ltd.) according to a formula ratio, extruding, cooling, granulating and drying to obtain the flame-retardant degradable low-melting-point polyester chip;
the parameters of the double-screw extruder are as follows: the six heating zones have the temperature of 160 ℃, 165 ℃, 168 ℃, 172 ℃ and 168 ℃, the rotating speed of a main machine is 250r/min, the aperture of the filter screen is 60 mu m, and the pressure is 12 MPa.
The obtained slices are made into strip samples in a molten state, and the measured limiting oxygen index is 29.4 percent; the degradation performance is also greatly improved.
Example 3
The flame-retardant degradable low-melting-point polyester chip comprises the following raw materials:
0.31kg of flame retardant and 2.27kg of low-melting-point polyester chips;
wherein, the flame retardant is prepared by blending the following components:
0.16kg of nano-magnesium hydroxide, 0.15kg of nano-antimony trioxide and 4.65g of maleic anhydride polyethylene wax graft serving as a coupling agent;
the low-melting-point polyester chip is obtained by esterification and polycondensation reaction of the following components:
PTA 2.22kg, EG 1.07L, diethylene glycol 0.239kg, ethylene glycol antimony 2.04 g.
The preparation method comprises the following steps:
(1) preparation of Low melting polyester chips
Weighing PTA, EG, diethylene glycol and ethylene glycol antimony according to a formula proportion, adding the PTA, EG, diethylene glycol and ethylene glycol antimony into a 5L polymerization reaction kettle (GSH-5 type 5L polymerization reaction kettle, Winhalaxing rain chemical equipment Co., Ltd.), starting a stirring motor (Shandong Zibobos Subo micromotor Co., Ltd., model 130SZ02A1), carrying out esterification reaction under the pressure of 0.2MPa and the temperature of 250 ℃, calculating to obtain the theoretical water yield of 347ml according to the acid-base neutralization reaction quality conservation principle, finishing the esterification reaction when the distilled water amount reaches about 330ml, carrying out polycondensation reaction for 1h under the conditions of vacuum degree of 255Pa and the temperature of 265 ℃, and then gradually transferring to the conditions of vacuum degree of 50Pa and the temperature of 280 ℃ to continue the polycondensation reaction for 3 h; when the power value of the stirring motor reaches 75W, discharging, cooling, granulating and drying to obtain the low-melting-point polyester chip;
(2) preparation of flame retardant
Weighing nanoscale magnesium hydroxide and nanoscale antimony trioxide according to a formula ratio, mixing in a high-speed kneader (MHZ-5L electric heating vacuum kneader manufactured by Nanhai Jinchuntai mechanical equipment Co., Ltd., Fushan City) for 5min, adding a maleic anhydride polyethylene wax graft serving as a coupling agent, continuously mixing for 15min, and discharging to obtain the flame retardant;
the parameters of the high-speed kneader are set as follows: the temperature is 150 ℃, and the speed is 1500 rpm/min;
(3) adding the low-melting-point polyester chip prepared in the step (1) and the flame retardant prepared in the step (2) into a double-screw extruder (TSE 65 type co-rotating double-screw extruder, Nanjing Kelida mechanical equipment Co., Ltd.) according to a formula ratio, extruding, cooling, granulating and drying to obtain the flame-retardant degradable low-melting-point polyester chip;
the parameters of the double-screw extruder are as follows: the six heating zones have the temperature of 155 ℃, 163 ℃, 166 ℃, 170 ℃ and 166 ℃, the rotating speed of a main engine of 300r/min, the aperture of a filter screen of 40 mu m and the pressure of 12MPa in sequence.
Preparing the obtained slices into strip samples in a molten state, and measuring the limiting oxygen index to be 28.2%; the degradation performance is also greatly improved.
Comparative example 1
Preparation and performance of conventional low-melting-point polyester chip
The low-melting-point polyester chip is obtained by esterification and polycondensation reaction of the following components:
PTA 2.01kg, EG 1.2L, diethylene glycol 0.134kg, ethylene glycol antimony 2.01 g.
The preparation method comprises the following steps:
weighing PTA, EG, diethylene glycol and ethylene glycol antimony according to a formula proportion, adding the PTA, EG, diethylene glycol and ethylene glycol antimony into a 5L polymerization reactor (GSH-5 type 5L polymerization reactor, Winhalay rain chemical equipment Co., Ltd.), starting a stirring motor, Shandong Zibobosan Subo micromotor Co., Ltd., model No. 130SZ02A1), carrying out esterification reaction under the conditions of 0.3MPa of pressure and 260 ℃ of initial power value of 28W, calculating out 390ml of theoretical water yield according to the conservation principle of acid-base neutralization reaction quality, finishing the esterification reaction when the distilled water amount reaches about 370ml, then carrying out polycondensation reaction for 1h under the conditions of 300Pa of vacuum degree and 268 ℃ of temperature, and then gradually switching to 30Pa of vacuum degree and 280 ℃ of temperature to continue the polycondensation reaction for 3 h; when the power value of the stirring motor reaches 78W, discharging, cooling, granulating and drying to obtain the low-melting-point polyester chip;
preparing the obtained low-melting-point polyester chip into a strip sample in a molten state, and measuring the limiting oxygen index to be 24.7%; the bars were substantially free of degradation.
Comparative example 2
Preparation and performance of flame-retardant low-melting-point polyester chip
The raw material formula of the flame-retardant low-melting-point polyester chip is as follows:
0.22kg of flame retardant and 2.53kg of low-melting-point polyester chips;
wherein, the flame retardant is prepared by blending the following components:
0.10kg of nano-magnesium hydroxide and 0.12kg of nano-antimony trioxide;
the low-melting-point polyester chip is obtained by esterification and polycondensation reaction of the following components:
PTA 2.01kg, EG 1.2L, diethylene glycol 0.134kg, ethylene glycol antimony 2.01 g.
The preparation method comprises the following steps:
(1) preparation of Low melting polyester chips
Weighing PTA, EG, diethylene glycol and ethylene glycol antimony according to a formula proportion, adding the PTA, EG, diethylene glycol and ethylene glycol antimony into a 5L polymerization reactor (GSH-5 type 5L polymerization reactor, Winhalay rain chemical equipment Co., Ltd.), starting a stirring motor, Shandong Zibobosan Subo micromotor Co., Ltd., model No. 130SZ02A1), carrying out esterification reaction under the conditions of 0.3MPa of pressure and 260 ℃ of initial power value of 28W, calculating out 390ml of theoretical water yield according to the conservation principle of acid-base neutralization reaction quality, finishing the esterification reaction when the distilled water amount reaches about 370ml, then carrying out polycondensation reaction for 1h under the conditions of 300Pa of vacuum degree and 268 ℃ of temperature, and then gradually switching to 30Pa of vacuum degree and 280 ℃ of temperature to continue the polycondensation reaction for 3 h; when the power value of the stirring motor reaches 78W, discharging, cooling, granulating and drying to obtain the low-melting-point polyester chip;
(2) preparation of flame retardant
Weighing nanoscale magnesium hydroxide and nanoscale antimony trioxide according to the formula proportion, and mixing in a high-speed kneader (MHZ-5L electric heating vacuum kneader manufactured by Nanhai Jinchuntai mechanical equipment Co., Ltd., Fushan City) for 5min to obtain the flame retardant;
the parameters of the high-speed kneader are set as follows: the temperature is 150 ℃, and the speed is 1500 rpm/min;
(3) adding the low-melting-point polyester chip prepared in the step (1) and the flame retardant prepared in the step (2) into a double-screw extruder (TSE 65 type co-rotating double-screw extruder, Nanjing Kelida mechanical equipment Co., Ltd.) according to a formula ratio, extruding, cooling, granulating and drying to obtain the flame-retardant degradable low-melting-point polyester chip;
the parameters of the double-screw extruder are as follows: the six heating zones have the temperature of 150 ℃, 160 ℃, 165 ℃, 168 ℃ and 165 ℃, the rotating speed of a main machine of 200r/min, the aperture of a filter screen of 30 mu m and the pressure of 10 MPa.
Preparing the obtained slices into strip samples in a molten state, measuring that the limiting oxygen index is 27.1 percent, and displaying that the flame retardant has an agglomeration phenomenon through electron microscope scanning, which indicates that the flame retardant is not uniformly dispersed in the low-melting-point polyester matrix; the bars were substantially free of degradation.
Claims (4)
1. The flame-retardant degradable low-melting-point polyester chip is characterized by being prepared by blending the following raw materials in percentage by mass:
8 to 12 percent of fire retardant
88 to 92 percent of low-melting-point polyester chip
Wherein,
the flame retardant is prepared by blending the following components in percentage by mass:
44-55% of nano-magnesium hydroxide, 43-54% of nano-antimony trioxide and 1-2% of maleic anhydride polyethylene wax graft serving as a coupling agent;
the low-melting-point polyester chip is obtained by esterification and polycondensation reaction of the following components:
purified terephthalic acid, ethylene glycol, diethylene glycol and ethylene glycol antimony;
based on the total mass of the purified terephthalic acid and the ethylene glycol, the mass percent of the purified terephthalic acid is 60-65%, and the mass percent of the ethylene glycol is 35-40%;
the mass usage of the diethylene glycol is 10-20% of the mass of the ethylene glycol;
the mass consumption of the ethylene glycol antimony is 0.1-0.2% of the mass of the purified terephthalic acid.
2. The method for preparing the flame-retardant degradable low-melting-point polyester chip according to claim 1, wherein the method comprises the following steps:
(1) preparation of Low melting polyester chips
Weighing purified terephthalic acid, ethylene glycol, diethylene glycol and ethylene glycol antimony according to a formula ratio, adding the weighed purified terephthalic acid, ethylene glycol, diethylene glycol and ethylene glycol antimony into a polymerization reaction kettle, starting a stirring motor, wherein the initial power value is 25-28W, carrying out esterification reaction under the conditions of pressure of 0.2-0.3 MPa and temperature of 250-260 ℃, finishing the esterification reaction when the theoretical water yield reaches more than 95%, then carrying out polycondensation reaction for 1-1.5 hours under the conditions of vacuum degree of 250-300 Pa and temperature of 265-270 ℃, and then continuing the polycondensation reaction for 2.5-3 hours under the conditions of vacuum degree of 30-50 Pa and temperature of 275-280 ℃; when the power value of the stirring motor reaches 75-78W, discharging, cooling, granulating and drying to obtain the low-melting-point polyester chip;
(2) preparation of flame retardant
Weighing nanoscale magnesium hydroxide and nanoscale antimony trioxide according to the formula proportion, mixing in a high-speed kneading machine for 5-10 min, adding a coupling agent maleic anhydride polyethylene wax graft, continuously mixing for 15-20 min, and discharging to obtain the flame retardant;
(3) and (3) adding the low-melting-point polyester chip prepared in the step (1) and the flame retardant prepared in the step (2) into a double-screw extruder according to the formula ratio for extrusion, and then cooling, granulating and drying to obtain the flame-retardant degradable low-melting-point polyester chip.
3. The production method according to claim 2, wherein in the step (2), the parameters of the high-speed kneader are set to: the temperature is 130-170 ℃ and the speed is 28-42 rpm/min.
4. The method according to claim 2, wherein in the step (3), the parameters of the twin-screw extruder are set as follows: the temperatures of the heating zones were as follows: the temperature of the first zone is 150-160 ℃, the temperature of the second zone is 160-165 ℃, the temperature of the third zone is 165-168 ℃, the temperature of the fourth zone is 165-168 ℃, the temperature of the fifth zone is 168-172 ℃, the temperature of the sixth zone is 168-165 ℃, the rotating speed of a main engine is 200-300 r/min, the aperture of a filter screen is 30-60 mu m, and the pressure is 10-12 MPa.
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| CN110016212A (en) * | 2019-05-06 | 2019-07-16 | 宿迁逸达新材料有限公司 | A kind of low melting point polyester chip preparation process |
| CN113699603A (en) * | 2021-08-23 | 2021-11-26 | 潘显双 | Preparation method of heat-preservation porous fine denier fiber |
| CN114605468A (en) * | 2022-01-21 | 2022-06-10 | 太原科技大学 | Preparation method and application of bio-based flame-retardant compatilizer for PBAT |
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| CN105384921A (en) * | 2015-11-04 | 2016-03-09 | 浙江恒逸高新材料有限公司 | Expansive-type inflaming retarding hydrophilic polyester (PET) chip and preparation method thereof |
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| CN102161751A (en) * | 2011-01-12 | 2011-08-24 | 江南大学 | Method for producing polyester sizing agent |
| CN102942686A (en) * | 2012-12-03 | 2013-02-27 | 安徽皖维高新材料股份有限公司 | Persian black silk ribbon flame-retardant polyester and preparation method thereof |
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| CN110016212A (en) * | 2019-05-06 | 2019-07-16 | 宿迁逸达新材料有限公司 | A kind of low melting point polyester chip preparation process |
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| CN114605468A (en) * | 2022-01-21 | 2022-06-10 | 太原科技大学 | Preparation method and application of bio-based flame-retardant compatilizer for PBAT |
| CN114605468B (en) * | 2022-01-21 | 2023-09-05 | 太原科技大学 | Preparation method and application of bio-based flame retardant compatilizer for PBAT (Poly (butylene succinate)) |
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