CN117343301A - Low-melting-point cationic dye easy-to-color PET resin and preparation method and application thereof - Google Patents
Low-melting-point cationic dye easy-to-color PET resin and preparation method and application thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 title claims abstract description 34
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 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 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 39
- GDYYIJNDPMFMTB-UHFFFAOYSA-N 2-[3-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC(CC(O)=O)=C1 GDYYIJNDPMFMTB-UHFFFAOYSA-N 0.000 claims abstract description 37
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- FCODQYLSDNRUBJ-UHFFFAOYSA-N 3-phenylpentane-1,5-diol Chemical compound OCCC(CCO)C1=CC=CC=C1 FCODQYLSDNRUBJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 15
- 229940011182 cobalt acetate Drugs 0.000 claims description 15
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 15
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical group [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 11
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000004040 coloring Methods 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 abstract description 31
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 29
- 229920000139 polyethylene terephthalate Polymers 0.000 description 21
- 239000005020 polyethylene terephthalate Substances 0.000 description 21
- 239000000975 dye Substances 0.000 description 17
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a low-melting-point cationic dye easy-to-color PET resin, and a preparation method and application thereof, belonging to the technical field of polyester molecule synthesis; a low-melting-point cationic dye easy-to-color PET resin comprises the following raw materials: terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol and PEG, the molar ratio is 0.82-0.85:0.1-0.13:0.04-0.06:1.04-1.12:0.06-0.08:0.1-0.16; the low-melting-point cationic dye easy-to-color PET resin is prepared from the following components in percentage by weight: adding the raw materials, an antimony catalyst, a titanium catalyst, a stabilizer and a toner into a reaction kettle, replacing with nitrogen, performing esterification reaction, and performing polycondensation reaction to obtain the catalyst; the obtained resin has low melting point and is easy to color.
Description
Technical Field
The invention belongs to the technical field of polyester molecule synthesis, and particularly relates to a low-melting-point cationic dye easy-to-color PET resin, and a preparation method and application thereof.
Background
Low melting point polyesters are a special type of modified copolyester with a melting point lower than the melting point range of conventional polyesters (polyethylene terephthalate, PET for short), typically between 90 and 240 degrees celsius. When the low-melting-point polyester is prepared, the ordered arrangement of molecular chains is broken through introducing some modifying components, and the rigid structure of polyester molecules is changed, so that the melting point of the polyester is reduced. Since the chemical structure of the low melting polyester is similar to that of conventional polyesters, it retains some of the characteristics of conventional polyesters. In addition, it has the advantages of excellent compatibility, good fluidity, low melting point, etc., and thus is widely used in various fields such as manufacturing filters, polyester color master batches, non-woven fabrics, and weaving of synthetic fibers.
Because the polyester molecular chain contains a large number of benzene rings, the ester groups with strong water absorption capacity are difficult to combine with water molecules due to the steric hindrance effect of the benzene rings; secondly, the high regularity of the polyester molecular chain makes the polyester molecular chain structure compact, and water molecules are difficult to diffuse into, so that the polyester shows hydrophobicity. Moreover, polyester PET lacks groups and hydrophilic groups capable of being combined with dyes, and can be dyed under the condition of high temperature and high pressure, so that dyeing is difficult.
Therefore, the problem of how to introduce a group capable of binding to a dye and a hydrophilic group into a polyester molecular segment and to lower the melting point of the polyester is very important.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-melting-point cationic dye easy-to-color PET resin, and a preparation method and application thereof, and solves the problems in the prior art.
The aim of the invention can be achieved by the following technical scheme:
a low-melting-point cationic dye easy-to-color PET resin comprises the following raw materials: terephthalic acid, 1, 3-benzenediacetic acid, sodium isophthalic acid-5-sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, and PEG.
Wherein, 3-phenylpentane-1, 5-diol is purchased from Xiang Hui medicine, and the product number is: CB17224, CAS number 829-27-6, has the structural formula:
the low-melting-point cationic dye easy-to-color PET resin is prepared from the following components in percentage by weight: adding the raw materials, an antimony catalyst, a titanium catalyst, a stabilizer and a toner into a reaction kettle, replacing with nitrogen, performing esterification reaction, and performing polycondensation reaction to obtain the catalyst; wherein the molar ratio of the raw materials is 0.82-0.85:0.1-0.13:0.04-0.06:1.04-1.12:0.06-0.08:0.1-0.16.
The titanium catalyst is tetrabutyl titanate; the antimony catalyst is ethylene glycol antimony or antimony acetate, and the stabilizer is phosphoric acid, trimethyl phosphate or triphenyl phosphate; the toner is cobalt acetate.
The adding amount of the antimony catalyst is 50-100 ppm of the total mass of terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate, the adding amount of the titanium catalyst is 100-150 ppm of the total mass of terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate, the adding amount of the stabilizer is 100-170 ppm of the total mass of terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate, and the adding amount of the toner is 150-240 ppm of the total mass of terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate.
The number average molecular weight of PEG is 200-400.
The esterification reaction is as follows: reacting under nitrogen atmosphere with the temperature of 250-255 ℃ and the pressure of 0.3 MPa; the temperature of the polycondensation reaction is 270-275 ℃ and the high vacuum is 65-70 Pa.
A preparation method of a low-melting-point cationic dye easy-to-color PET resin comprises the following steps:
s1, preparing slurry from terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG, antimony catalyst, titanium catalyst, stabilizer and toner, adding into a reaction kettle, and carrying out esterification reaction under the nitrogen atmosphere with the temperature of 250-255 ℃ and the pressure of 0.3 MPa; wherein, the mol ratio of terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol and PEG is 0.82-0.85:0.1-0.13:0.04-0.06:1.04-1.12:0.06-0.08:0.1-0.16;
s2, reacting for 40min at 255 ℃ in the kettle and automatically heating to 270-275 ℃ under the pressure of minus 0.1MPa, and reacting for 90min at 270-275 ℃ under the high vacuum of 65-70 Pa to obtain the low-melting-point cationic dye easy-coloring PET resin.
The application of the PET resin in preparing BOPET heat-sealing films.
The invention has the beneficial effects that:
1. according to the invention, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate copolymerization modified monomers are added into the synthetic raw materials of conventional polyester, so that the regularity of the molecular weight of the polyester can be destroyed, and the purpose of reducing the melting point of the polyester is achieved;
2. the isophthalic acid-5-sodium sulfonate introduces sulfonic acid groups capable of being combined with dye molecules through ionic bonds into polyester molecules by a copolymerization method to prepare master batches with high content;
3. the isophthalic acid-5-sodium sulfonate can introduce ionic bonds to form ion clusters (which is equivalent to increasing crosslinking points), so that the activity of a polyester molecular chain segment is inhibited, the glass transition temperature of the polyester is improved, and the phenomenon of adhesion can be avoided;
4. adding 3-phenylpentane-1, 5-diol copolymerization modified monomer into the synthetic raw material of conventional polyester, wherein the benzene ring of the side group increases the distance between molecular chains, and the molecular chains have larger space for movement, so that the glass transition temperature of the copolyester is reduced; the side group benzene ring also has steric hindrance effect, so that the melting point is reduced;
5. the addition of polyethylene glycol (PEG) effectively improves the rheological property of the functional polyester, and is beneficial to improving the crystallinity of the functional polyester which is reduced by the addition of the modified diacid monomer.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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 following examples 1-5 illustrate the preparation of a low melting cationic dye-ready-to-color PET resin:
example 1
S1, esterification reaction;
terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG-400, ethylene glycol antimony, tetrabutyl titanate, trimethyl phosphate and cobalt acetate are prepared into slurry, and then added into a reaction kettle to react under the nitrogen atmosphere with the temperature of 250 ℃ and the pressure of 0.3MPa until the water distillate reaches 95% of theoretical value; wherein the molar ratio of terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol and PEG-400 is 0.85:0.1:0.05:1.09:0.06:0.1; the mass addition amount of ethylene glycol antimony is 80ppm of the total mass of diacid monomers (terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate), the mass addition amount of tetrabutyl titanate is 120 ppm of the total mass of diacid monomers, the mass addition amount of trimethyl phosphate is 170ppm of the total mass of diacid monomers, and the mass addition amount of cobalt acetate is 150ppm of the total mass of diacid monomers.
S2, performing polycondensation reaction;
at 255 ℃ in the kettle, automatically heating to 270 ℃ and reacting for 40min under the pressure of-0.1 MPa, and reacting for 90min under the temperature of 270 ℃ and the high vacuum of 70Pa to obtain the low-melting-point cationic dye easy-to-color PET resin.
Example 2
S1, esterification reaction;
terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG-200, antimony acetate, tetrabutyl titanate, triphenyl phosphate and cobalt acetate are prepared into slurry, and then the slurry is added into a reaction kettle to react under the nitrogen atmosphere with the temperature of 255 ℃ and the pressure of 0.3MPa until the water distillate reaches 95% of theoretical value; wherein, the mol ratio of terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, glycol, 3-phenylpentane-1, 5-diol and PEG-200 is 0.84:0.1:0.06:1.12:0.08:0.11; the mass addition amount of the antimony acetate is 100ppm of the total mass of diacid monomers (terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate), the mass addition amount of the tetrabutyl titanate is 100ppm of the total mass of diacid monomers, the mass addition amount of the triphenyl phosphate is 100ppm of the total mass of diacid monomers, and the mass addition amount of the cobalt acetate is 240ppm of the total mass of diacid monomers.
S2, performing polycondensation reaction;
the low-melting-point cationic dye easy-coloring PET resin is prepared after the reaction for 40min under the conditions that the temperature in a kettle is 255 ℃, the temperature is automatically increased to 275 ℃ and the pressure is minus 0.1MPa, and the reaction for 90min under the conditions that the temperature is 275 ℃ and the high vacuum is 65 Pa.
Example 3
S1, esterification reaction;
terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG-200, ethylene glycol antimony, tetrabutyl titanate, phosphoric acid and cobalt acetate are prepared into slurry, and then the slurry is added into a reaction kettle to react under the nitrogen atmosphere with the temperature of 253 ℃ and the pressure of 0.3MPa until the water distillate reaches 95% of theoretical value; wherein, the mol ratio of terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, glycol, 3-phenylpentane-1, 5-diol and PEG-200 is 0.83:0.11:0.06:1.11:0.07:0.13; the mass addition amount of ethylene glycol antimony is 50ppm of the total mass of diacid monomers (terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate), the mass addition amount of tetrabutyl titanate is 150ppm of the total mass of diacid monomers, the mass addition amount of phosphoric acid is 120 ppm of the total mass of diacid monomers, and the mass addition amount of cobalt acetate is 200 ppm of the total mass of diacid monomers.
S2, performing polycondensation reaction;
the low-melting-point cationic dye easy-coloring PET resin is prepared after the reaction for 40min under the conditions that the temperature in a kettle is 255 ℃, the temperature is automatically increased to 273 ℃ and the pressure is minus 0.1MPa, and the reaction for 90min under the conditions that the temperature is 273 ℃ and the high vacuum is 67 Pa.
Example 4
S1, esterification reaction;
terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG-200, ethylene glycol antimony, tetrabutyl titanate, trimethyl phosphate and cobalt acetate are prepared into slurry, and then added into a reaction kettle to react under the nitrogen atmosphere with the temperature of 253 ℃ and the pressure of 0.3MPa until the water distillate reaches 95% of theoretical value; wherein, the mol ratio of terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, glycol, 3-phenylpentane-1, 5-diol and PEG-200 is 0.83:0.12:0.05:1.04:0.06:0.15; the mass addition amount of ethylene glycol antimony is 80ppm of the total mass of diacid monomers (terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate), the mass addition amount of tetrabutyl titanate is 120 ppm of the total mass of diacid monomers, the mass addition amount of trimethyl phosphate is 150ppm of the total mass of diacid monomers, and the mass addition amount of cobalt acetate is 200 ppm of the total mass of diacid monomers.
S2, performing polycondensation reaction;
the low-melting-point cationic dye easy-coloring PET resin is prepared after the reaction for 40min under the conditions that the temperature in the kettle is 255 ℃, the temperature is automatically increased to 273 ℃ and the pressure is minus 0.1MPa, and the reaction for 90min under the conditions that the temperature is 273 ℃ and the high vacuum is 66 Pa.
Example 5
S1, esterification reaction;
terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG-200, ethylene glycol antimony, tetrabutyl titanate, trimethyl phosphate and cobalt acetate are prepared into slurry, and then added into a reaction kettle to react under the nitrogen atmosphere with the temperature of 253 ℃ and the pressure of 0.3MPa until the water distillate reaches 95% of theoretical value; wherein, the mol ratio of terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, glycol, 3-phenylpentane-1, 5-diol and PEG-200 is 0.83:0.13:0.04:1.08:0.07:0.16; the mass addition amount of ethylene glycol antimony is 80ppm of the total mass of diacid monomers (terephthalic acid, 1, 3-benzene diacetic acid and isophthalic acid-5-sodium sulfonate), the mass addition amount of tetrabutyl titanate is 120 ppm of the total mass of diacid monomers, the mass addition amount of trimethyl phosphate is 150ppm of the total mass of diacid monomers, and the mass addition amount of cobalt acetate is 200 ppm of the total mass of diacid monomers.
S2, performing polycondensation reaction;
the low-melting-point cationic dye easy-coloring PET resin is prepared after the reaction for 40min under the conditions that the temperature in a kettle is 255 ℃, the temperature is automatically increased to 273 ℃ and the pressure is minus 0.1MPa, and the reaction for 90min under the conditions that the temperature is 273 ℃ and the high vacuum is 67 Pa.
Comparative example 1
S1, esterification reaction;
preparing terephthalic acid, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG-200, ethylene glycol antimony, tetrabutyl titanate, trimethyl phosphate and cobalt acetate into slurry, adding the slurry into a reaction kettle, and reacting in a nitrogen atmosphere with the temperature of 253 ℃ and the pressure of 0.3MPa until the water distillate reaches 95% of theoretical value; wherein, the mol ratio of terephthalic acid, ethylene glycol, 3-phenylpentane-1, 5-diol and PEG-200 is 1:1.08:0.07:0.16; the mass addition amount of ethylene glycol antimony is 80ppm of the total mass of diacid monomer (terephthalic acid), the mass addition amount of tetrabutyl titanate is 120 ppm of the total mass of diacid monomer, the mass addition amount of trimethyl phosphate is 150ppm of the total mass of diacid monomer, and the mass addition amount of cobalt acetate is 200 ppm of the total mass of diacid monomer.
(2) Performing polycondensation reaction;
the low-melting-point cationic dye easy-coloring PET resin is prepared after the reaction for 40min under the conditions that the temperature in a kettle is 255 ℃, the temperature is automatically increased to 273 ℃ and the pressure is minus 0.1MPa, and the reaction for 90min under the conditions that the temperature is 273 ℃ and the high vacuum is 67 Pa.
Performance testing
The properties of the low melting cationic dye pigmentable PET resins provided in examples 1-5 and comparative example 1 above were subjected to the relevant parametric tests, the test results being shown in Table 1.
From the data in table 1, it can be seen that:
from the data of the examples and comparative examples, it can be seen that the addition of 1, 3-benzenediacetic acid and sodium isophthalic acid-5-sulfonate greatly reduced the melting point of the polyester. The addition of PEG breaks the regularity of molecular chains, increases the distance between macromolecules, reduces the intermolecular acting force, and ensures good flexibility of macromolecules due to the introduction of long carbon chain dihydric alcohol. Compared with the conventional large-gloss polyester PET chips, the benzene ring of the side group of the 3-phenylpentane-1, 5-diol increases the distance between molecular chains, and the molecular chains have larger space to move, so that the modified diacid monomer (1, 3-phenylpentane-1, 5-diol and PEG) is obviously used for reducing the melting point of the polyester PET.
As can be seen from comparison of the performance data of example 5 and comparative example 1, the addition of the modified diacid monomer (1, 3-benzenediacetic acid, isophthalic acid-5-sodium sulfonate) caused the deterioration of the regularity of the polyester macromolecular chain, reduced the intermolecular force, increased the randomness and decreased the melting enthalpy, thereby realizing the melting point reduction.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (11)
1. The low-melting-point cationic dye easy-to-color PET resin is characterized by comprising the following raw materials: terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol and PEG, the molar ratio is 0.82-0.85:0.1-0.13:0.04-0.06:1.04-1.12:0.06-0.08:0.1-0.16;
the low-melting-point cationic dye easy-to-color PET resin is prepared by adding the raw materials, a catalyst, a stabilizer and a toner into a reaction kettle, replacing with nitrogen, performing esterification reaction, and performing polycondensation reaction.
2. The low melting point cationic dye pigmentable PET resin of claim 1, wherein the catalyst comprises: antimony-based catalysts and titanium-based catalysts.
3. The low-melting cationic dye-sensitized PET resin according to claim 2, wherein the titanium catalyst is tetrabutyl titanate; the antimony catalyst is ethylene glycol antimony or antimony acetate, and the stabilizer is phosphoric acid, trimethyl phosphate or triphenyl phosphate; the toner is cobalt acetate.
4. The low-melting point cationic dye-easily colored PET resin according to claim 2, wherein the antimony-based catalyst is added in an amount of 50 to 100ppm based on the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate, the titanium-based catalyst is added in an amount of 100 to 150ppm based on the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate, the stabilizer is added in an amount of 100 to 170ppm based on the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate, and the toner is added in an amount of 150 to 240ppm based on the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate.
5. The low melting point cationic dye pigmentable PET resin of claim 1, wherein the PEG has a number average molecular weight of 200 to 400.
6. The low melting point cationic dye pigmentable PET resin of claim 2, wherein the esterification reaction is: reacting under nitrogen atmosphere with the temperature of 250-255 ℃ and the pressure of 0.3 MPa; the temperature of the polycondensation reaction is 270-275 ℃ and the high vacuum is 65-70 Pa.
7. The preparation method of the low-melting-point cationic dye easy-to-color PET resin is characterized by comprising the following steps of:
s1, preparing slurry from terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol, PEG, antimony catalyst, titanium catalyst, stabilizer and toner, adding into a reaction kettle, and carrying out esterification reaction under the nitrogen atmosphere with the temperature of 250-255 ℃ and the pressure of 0.3 MPa; wherein, the mol ratio of terephthalic acid, 1, 3-benzene diacetic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol, 3-phenylpentane-1, 5-diol and PEG is 0.82-0.85:0.1-0.13:0.04-0.06:1.04-1.12:0.06-0.08:0.1-0.16;
s2, reacting for 40min at 255 ℃ in the kettle and automatically heating to 270-275 ℃ under the pressure of minus 0.1MPa, and reacting for 90min at 270-275 ℃ under the high vacuum of 65-70 Pa to obtain the low-melting-point cationic dye easy-coloring PET resin.
8. The method for preparing a low-melting-point cationic dye-sensitized PET resin according to claim 7, wherein the titanium catalyst is tetrabutyl titanate; the antimony catalyst is ethylene glycol antimony or antimony acetate, and the stabilizer is phosphoric acid, trimethyl phosphate or triphenyl phosphate; the toner is cobalt acetate.
9. The method for preparing a low melting point cationic dye-colored PET resin according to claim 7, wherein the addition amount of the antimony-based catalyst is 50-100 ppm of the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate, the addition amount of the titanium-based catalyst is 100-150 ppm of the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate, the addition amount of the stabilizer is 100-170 ppm of the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate, and the addition amount of the toner is 150-240 ppm of the total mass of terephthalic acid, 1, 3-benzenediacetic acid and isophthalic acid-5-sodium sulfonate.
10. The method for preparing a low melting point cationic dye-sensitized PET resin according to claim 7, wherein PEG has a number average molecular weight of 200 to 400.
11. Use of the low-melting cationic dye-sensitized PET resin according to any one of claims 1 to 6 for preparing BOPET heat-seal films.
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