CN101130602A - Method for producing poly-p-benzene dicarboxylic acid trimethylene glycol ester - Google Patents
Method for producing poly-p-benzene dicarboxylic acid trimethylene glycol ester Download PDFInfo
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- CN101130602A CN101130602A CNA2006100862155A CN200610086215A CN101130602A CN 101130602 A CN101130602 A CN 101130602A CN A2006100862155 A CNA2006100862155 A CN A2006100862155A CN 200610086215 A CN200610086215 A CN 200610086215A CN 101130602 A CN101130602 A CN 101130602A
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- -1 poly-p-benzene dicarboxylic acid trimethylene glycol ester Chemical class 0.000 title claims description 62
- 238000004519 manufacturing process Methods 0.000 title description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N Trimethylene glycol Natural products OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title 1
- 229920000728 polyester Polymers 0.000 claims abstract description 33
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 25
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 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 14
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 14
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 22
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000379 polymerizing effect Effects 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003504 terephthalic acids Chemical class 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- GPXJTESFCFTLHT-UHFFFAOYSA-N 1,2-diphenylpropane-1,1-diol Chemical compound C=1C=CC=CC=1C(O)(O)C(C)C1=CC=CC=C1 GPXJTESFCFTLHT-UHFFFAOYSA-N 0.000 description 2
- IQVAERDLDAZARL-UHFFFAOYSA-N 2-phenylpropanal Chemical compound O=CC(C)C1=CC=CC=C1 IQVAERDLDAZARL-UHFFFAOYSA-N 0.000 description 2
- WCPAKUFSQFCWTQ-UHFFFAOYSA-N 3,4-diethyl-2,5-dimethylhexane Chemical compound CCC(C(C)C)C(CC)C(C)C WCPAKUFSQFCWTQ-UHFFFAOYSA-N 0.000 description 2
- LZFCEXJTLLKGPW-UHFFFAOYSA-N 5-ethyl-3-methyloctane Chemical compound CCCC(CC)CC(C)CC LZFCEXJTLLKGPW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000005324 Typha latifolia Nutrition 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- NUHCTOLBWMJMLX-UHFFFAOYSA-N bromothymol blue Chemical compound BrC1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=C(Br)C(O)=C(C(C)C)C=2)C)=C1C NUHCTOLBWMJMLX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 244000118869 coast club rush Species 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparing method of polyytrimethylene terephthalate alcohol, which is characterized by the following: proceeding esterification reaction for terephthalic acid and 1, 3-methyl glycol; getting the product; proceeding polycondensation reaction; adopting structural formula (B) titanium compounds as accelerant in the polycondensation reaction; adopting phosphoric compound of structural formula (A) as stabilizer. This invention adds anti-oxidant and cobalt compounds to additional color, which polyester chip possesses better color cast and good heat endurance.
Description
Technical field:
The present invention relates to a kind of production method of Poly(Trimethylene Terephthalate).
Background technology:
Polyester, particularly polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate owing to its machinery, physics, chemical property excellence, thereby are used widely in fiber, film and other layered products.At present, because it is marked down and obtain 1 on a large scale, ammediol, so Poly(Trimethylene Terephthalate) will be following a kind of up-and-coming plastics, it has long chain molecule structure and most of performance between ethylene glycol terephthalate and polybutylene terephthalate.The range of application that is fit to comprises whole fiber and molding field.But along with the expansion of its purposes and demand, strict all the more in every field to the characteristic requirement of polyester, so need the problem of solution also a lot.
The preparation process of polytrimethylene terephthalate need add catalyzer unlike polyethylene terephthalate in Esterification Stage, if do not add esterifying catalyst, the time will be very long; When if polycondensation catalyst uses the conventional polymerizing catalyst of polyethylene terephthalate, though can obtain having the polyester of good tone.But antimony compounds can cause a series of environmental problem, and to the preparation of Poly(Trimethylene Terephthalate), catalytic activity not enough, the reaction times will be elongated.
As the polymerizing catalyst of Poly(Trimethylene Terephthalate), adopt titanium compound, when adopting titanium compound, gained polyester self tone flavescence also has relatively poor hot melt stability.Usually, polyester because the processing temperature height, can be subjected to thermal oxidation and degrades when forming process, and molecular weight sharply descends, and causes goods embrittlement, and its colour changed into yellow loses use value.In addition, also flavescence gradually in long-term placement or use can't obtain light goods.
In order to improve tone, generally can add toning agents such as cobalt compound, but the melting heat of polyester stability reduces, the transparency also can reduce simultaneously, common Hinered phenols antioxidant and the phosphorous acid esters pro-oxidant of adding in addition.Only add triethyl 4 phosphorous acid esters as TOHKEMY 2004-43540, they have all improved the stability of goods in various degree, have improved the color and luster variation, but effect is also undesirable.
Summary of the invention:
The object of the present invention is to provide a kind of polyester that makes to have good color tone (b value), the preparation method of the Poly(Trimethylene Terephthalate) that the thermotolerance index is higher.
Technical solution of the present invention is:
A kind of preparation method of Poly(Trimethylene Terephthalate) comprises terephthalic acid and 1, and ammediol carries out esterification, and esterification reaction product carries out polycondensation again, it is characterized in that: esterification is catalyzer with the titanium compound; Adopting the titanium compound of following structural formula (B) in the polycondensation is catalyzer, and the phosphorus compound that adopts following structural formula (A) is a stablizer:
Wherein, the R1～R4 in the P contained compound [A] is that carbon is 4～25 alkyl, cycloalkyl or aryl radical; Example R1～R4 can be 3-methyl-5-ethyl octane, 2,5-dimethyl-3,4-diethyl hexane, lauryl, hard ester group, 2,3,7-trimethylammonium-5-ethyl octane, 2,4-dibutyl phenyl, octyl phenyl, phenyl nonyl, phenyl dihydroxyphenyl propane, phenyl isodecyl etc.
R5～R8 in the titanium compound [B] is the group of following structural formula:
R in the formula
9～R
11Be that hydrogen or carbon are 1～30 alkyl, ether, ketone group, hydroxyl, carboxyl, carbonyl, ester group or amido.Example Succinic Acid, hexanodioic acid, adjacent benzene dicarboxylic acid, terephthalic acid, vinyl-acetic ester, methyl-formiate, dimethyl malonate, pentyl acetate, methyl phenyl ketone, 2-phenylpropionaldehyde, salicylaldhyde, crotonic aldehyde, 3-phenylacrolein, carboxylic acid amine etc.
The used represented phosphorous acid ester of general formula (A) of stablizer is to make with following method or other ordinary methods:
The alcohol that makes with cocounut oil (wherein tetradecyl alcohol accounts for 70%, lauryl alcohol accounts for 30%) and dihydroxyphenyl propane and triphenyl phosphite reaction generation desired product and phenol are removed phenol again, obtain desired product.Wherein the cocounut oil composition is: caproic acid 0.2-0.5%, caprylic acid 5.4-9.5%, capric acid 4.5-9.7%, lauric acid 44.1-51.0%, beans tabernaemontanus bulrush acid 13.1-18.5%, palmitinic acid 7.5-10.5%, stearic acid 1.0-3.2%, eicosanoic acid 0.2-1.5%, oleic acid 5.0-8.2%, linolic acid 1.0-2.6%.
Catalyzer in the esterification is tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, titanium sulfate hydrolyzate or organic tin catalyzer.Also add Hinered phenols antioxidant in the polycondensation, routine Iragnox1010.Also add the toning agent cobalt compound in the polycondensation.The toning agent cobalt compound is a Cobaltous diacetate.With respect to final polyester product amount, titanium content is 0.01～0.1wt% in the catalyst for esterification reaction, and the titanium elements addition is 10～200ppm in the polycondensation catalyst, and the addition of phosphoric is 10～60ppm in the stablizer phosphorus compound; The addition of cobalt element is 20～60ppm in the toning agent cobalt compound.
The invention has the advantages that in preparation Poly(Trimethylene Terephthalate) process, by specified stabiliser and polycondensation catalyst effect, add oxidation inhibitor simultaneously and cobalt compound is mixed colours, the gained polyester slice has tone preferably, Heat stability is good.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Embodiment 1
A kind of method of production Poly(Trimethylene Terephthalate), comprise terephthalic acid and 1, ammediol carries out esterification, esterification reaction product carries out polycondensation again, wherein used catalyst for esterification reaction is tetrabutyl titanate (or titanium isopropylate, tetraethyl titanate, titanium sulfate hydrolyzate, organic tin catalyzer), adopting the titanium compound of following structural formula (B) in the polycondensation is catalyzer, and the phosphorus compound that adopts following structural formula (A) is a stablizer:
Wherein, the R1～R4 in the P contained compound [A] is that carbon is 4～25 alkyl, cycloalkyl or aryl radical; Example R1～R4 can be 3-methyl-5-ethyl octane, 2,5-dimethyl-3,4-diethyl hexane, lauryl, hard ester group, 2,3,7-trimethylammonium-5-ethyl octane, 2,4-dibutyl phenyl, octyl phenyl, phenyl nonyl, phenyl dihydroxyphenyl propane, phenyl isodecyl etc.
R5～R8 in the titanium compound [B] is the group of following structural formula:
R in the formula
9～R
11Be that hydrogen or carbon are 1～30 alkyl, ether, ketone group, hydroxyl, carboxyl, carbonyl, ester group or amido.Example Succinic Acid, hexanodioic acid, adjacent benzene dicarboxylic acid, terephthalic acid, vinyl-acetic ester, methyl-formiate, dimethyl malonate, pentyl acetate, methyl phenyl ketone, 2-phenylpropionaldehyde, salicylaldhyde, crotonic aldehyde, 3-phenylacrolein, carboxylic acid amine etc.
The chemical formula that is specifically related to as: phosphorus compound is following compound:
Titanium compound as:
Also add Hinered phenols antioxidant in the polycondensation, routine Iragnox1010.Also add toning agent cobalt compound---Cobaltous diacetate in the polycondensation.
Concrete reaction process is as follows:
Under 250 ℃ temperature, make 166 parts of (weight) terephthalic acids and 92 parts of (weight) 1, ammediol carries out the direct esterification reaction, add 0.086 part of tetrabutyl titanate (or above-mentioned other catalyzer) simultaneously and make esterifying catalyst, the gained reaction product is placed the polymerization test tube, and with titanium compound [B] 10ppm (with respect to the compound atomic mass of final polyester product weight) as polymerizing catalyst, phosphorus compound [A] 40ppm (with respect to the compound atomic mass of final polyester product weight) as stablizer, the addition of IR1010 is 0.166 part, mix, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature rises to 267 ℃ through half an hour, when described reaction is finished, temperature of reaction system is 267 ℃, and resulting pressure is about 200Pa, and the gained polyester inherent viscosity is between 0.90～0.93.
Embodiment 2:
With respect to final polyester product amount, the addition of titanium elements is 40ppm in the polycondensation catalyst, and the addition of phosphoric is 40ppm in the stablizer phosphorus compound.All the other are with embodiment 1.
Embodiment 3:
Also add toning agent cobalt compound---Cobaltous diacetate in the polycondensation.
With respect to final polyester product amount, the addition of titanium elements is 60ppm in the polycondensation catalyst, and the addition of phosphoric is 40ppm in the stablizer phosphorus compound, and the addition of cobalt element is 30ppm in the toning agent cobalt compound, and all the other are with embodiment 1.
Embodiment 4:
With respect to final polyester product amount, the addition of titanium elements is 80ppm in the polycondensation catalyst, and the addition of phosphoric is 40ppm in the stablizer phosphorus compound, and the addition of cobalt element is 30ppm in the toning agent cobalt compound, and all the other are with embodiment 3.
Embodiment 5:
With respect to final polyester product amount, the addition of titanium elements is 120ppm in the polycondensation catalyst, and the addition of phosphoric is 30ppm in the stablizer phosphorus compound, and the addition of cobalt element is 45ppm in the toning agent cobalt compound, and all the other are with embodiment 3.
Embodiment 6:
With respect to final polyester product amount, the addition of titanium elements is 160ppm in the polycondensation catalyst, and the addition of phosphoric is 45ppm in the stablizer phosphorus compound, and the addition of cobalt element is 35ppm in the toning agent cobalt compound, and all the other are with embodiment 3.
Embodiment 7:
With respect to final polyester product amount, the addition of titanium elements is 80ppm in the polycondensation catalyst, and the addition of phosphoric is 45ppm in the stablizer phosphorus compound, and the addition of cobalt element is 25ppm in the toning agent cobalt compound, and all the other are with embodiment 3.
Comparative example 1:
Under 250 ℃ temperature, make 166 parts of (weight) terephthalic acids and 92 parts of (weight) 1, ammediol carries out the direct esterification reaction, add 0.086 part of tetrabutyl titanate simultaneously and make esterifying catalyst, the gained reaction product is placed the polymerization test tube, and with titanium compound (with embodiment 1) 80ppm as polymerizing catalyst, toning agent cobalt compound---Cobaltous diacetate 30ppm, phosphatase 24 0ppm (wherein addition is the compound atomic mass with respect to final polyester product weight) as stablizer mixes, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature rises to 267 ℃ through half an hour, when described reaction is finished, temperature of reaction system is 267 ℃, resulting pressure is about 200Pa, and gained polyester viscosity is about 0.92.
Comparative example 2:
Under 250 ℃ temperature, make 166 parts of (weight) terephthalic acids and 92 parts of (weight) 1, ammediol carries out the direct esterification reaction, add 0.086 part of tetrabutyl titanate simultaneously and make esterifying catalyst, the gained reaction product is placed the polymerization test tube, and with antimonous oxide 300ppm as polymerizing catalyst, phosphatase 24 0ppm as stablizer, toning agent Cobaltous diacetate 100ppm (wherein addition is the compound atomic mass with respect to final polyester product weight) mixes, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature rises to 267 ℃ through half an hour, when described reaction is finished, temperature of reaction system is 267 ℃, resulting pressure is about 200Pa, and gained polyester viscosity is about 0.92.
| Numbering | Polyester properties | ||||||
| IV | COO H | The b value | Reclosing time | The damaged number of main chain (equivalent/1000 kilogram) | Be attached on the height of melt-spun mouth of pipe tramp material layer on every side | ||
| Embodiment | 1 | 0.908 | 19.5 | 8.5 | 2:48 | 2.5 | 4 |
| 2 | 0.920 | 18.7 | 8.8 | 2:43 | 2.8 | 6 | |
| 3 | 0.906 | 19.7 | 5.2 | 2:29 | 3.4 | 8 | |
| 4 | 0.918 | 20.8 | 5.8 | 2:25 | 3.5 | 5 | |
| 5 | 0.915 | 19.6 | 5.9 | 2:11 | 3.7 | 7 | |
| 6 | 0.909 | 21.2 | 6.4 | 2:05 | 3.3 | 6 | |
| 7 | 0.912 | 19.5 | 6.1 | 2:28 | 2.9 | 4 | |
| Comparative example | 1 | 0.913 | 23.1 | 10.8 | 2:56 | 4.2 | 9 |
| 2 | 0.901 | 20.5 | 4.4 | 2:21 | 2.6 | 46 | |
The measuring method of each index of the foregoing description 1～7, comparative example 1～4 is:
(1) limiting viscosity (IV) (dL/g)
With 0.5 gram polyester/milliliter phenol and sym.-tetrachloroethane etc. in the solution of weight mixture, in 25 ℃ of mensuration its limiting viscosities (IV) down
(2) melting heat stability
Polyester granules is put into 10 mm outer diameter of the nitrogen atmosphere that places 290 ℃, thus in the Glass tubing of 8 millimeters internal diameters, 250 mm lengths 15 minutes with its fusing.Before aforesaid thermal treatment and afterwards, measure the difference of the limiting viscosity of polyester granules.By the difference of limiting viscosity, the damaged number (equivalent) of the polyester molecule main chain of per 1000 kilograms of polyester polymers calculates according to following equation:
The damaged number of main chain (equivalent/1000 kilogram)
＝{[IV
1/3.07*10
-4]
-1.30-[IV
0/3.07*10
-4]
-1.30}*10
-6
In the equation, IV
0Represent the limiting viscosity of the preceding polyester of thermal treatment, IV
1Represent the limiting viscosity of polyester after the thermal treatment.
(3) carboxyl-content (COOH):
Adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70: 30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, carry out titration in the ethanolic soln with the potassium hydroxide of 0.05N then
(4) tone b value
Measure by GB GB/T 14190-1993.
Claims (6)
1. the preparation method of a Poly(Trimethylene Terephthalate), comprise terephthalic acid and 1, ammediol carries out esterification, esterification reaction product carries out polycondensation again, it is characterized in that: adopting the titanium compound of following structural formula (B) in the polycondensation is catalyzer, and the phosphorus compound that adopts following structural formula (A) is a stablizer:
Wherein, the R1～R4 in the P contained compound [A] is that carbon is 4～25 alkyl, cycloalkyl or aryl radical; R5～R8 in the titanium compound [B] is the group of following structural formula:
R in the formula
9～R
11Be that hydrogen or carbon are 1～30 alkyl, ether, ketone group, hydroxyl, carboxyl, carbonyl, ester group or amido.
2. the preparation method of Poly(Trimethylene Terephthalate) according to claim 1, it is characterized in that: the catalyzer in the esterification is tetrabutyl titanate, titanium isopropylate, tetraethyl titanate, titanium sulfate hydrolyzate or organic tin catalyzer.
3. the preparation method of Poly(Trimethylene Terephthalate) according to claim 1 and 2 is characterized in that: also add Hinered phenols antioxidant in the polycondensation.
4. the preparation method of Poly(Trimethylene Terephthalate) according to claim 1 and 2 is characterized in that: also add the toning agent cobalt compound in the polycondensation.
5. the preparation method of Poly(Trimethylene Terephthalate) according to claim 4, it is characterized in that: the toning agent cobalt compound is a Cobaltous diacetate.
6. the preparation method of Poly(Trimethylene Terephthalate) according to claim 5, it is characterized in that: with respect to final polyester product amount, titanium content is 0.01～0.1wt% in the catalyst for esterification reaction, the titanium elements addition is 10～200ppm in the polycondensation catalyst, and the addition of phosphoric is 10～60ppm in the stablizer phosphorus compound; The addition of cobalt element is 20～60ppm in the toning agent cobalt compound.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100862155A CN101130602A (en) | 2006-08-22 | 2006-08-22 | Method for producing poly-p-benzene dicarboxylic acid trimethylene glycol ester |
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|---|---|---|---|
| CNA2006100862155A CN101130602A (en) | 2006-08-22 | 2006-08-22 | Method for producing poly-p-benzene dicarboxylic acid trimethylene glycol ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167804A (en) * | 2011-03-05 | 2011-08-31 | 佛山塑料集团股份有限公司 | Preparation method of colored polyester chips |
| CN102181046A (en) * | 2011-03-05 | 2011-09-14 | 佛山塑料集团股份有限公司 | Preparation method of polyester chips for tangle film |
| CN104558552A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of poly(propylidene terephthalate) |
| CN114891189A (en) * | 2022-06-30 | 2022-08-12 | 中国天辰工程有限公司 | Preparation method of low-chroma PETG copolyester |
-
2006
- 2006-08-22 CN CNA2006100862155A patent/CN101130602A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167804A (en) * | 2011-03-05 | 2011-08-31 | 佛山塑料集团股份有限公司 | Preparation method of colored polyester chips |
| CN102181046A (en) * | 2011-03-05 | 2011-09-14 | 佛山塑料集团股份有限公司 | Preparation method of polyester chips for tangle film |
| CN104558552A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of poly(propylidene terephthalate) |
| CN114891189A (en) * | 2022-06-30 | 2022-08-12 | 中国天辰工程有限公司 | Preparation method of low-chroma PETG copolyester |
| CN114891189B (en) * | 2022-06-30 | 2023-10-31 | 中国天辰工程有限公司 | Preparation method of low-chroma PETG copolyester |
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