CN1065857C - Non-chemical nucleation type polyester nucleator and its preparing process and use - Google Patents
Non-chemical nucleation type polyester nucleator and its preparing process and use Download PDFInfo
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- CN1065857C CN1065857C CN96109004A CN96109004A CN1065857C CN 1065857 C CN1065857 C CN 1065857C CN 96109004 A CN96109004 A CN 96109004A CN 96109004 A CN96109004 A CN 96109004A CN 1065857 C CN1065857 C CN 1065857C
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- Prior art keywords
- nucleator
- pet
- terephthalate
- chemical
- type polyester
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- 229920000728 polyester Polymers 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000010899 nucleation Methods 0.000 title claims description 15
- 230000006911 nucleation Effects 0.000 title claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 terephthalate monocarboxylic acid alkali metal salt Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 28
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002667 nucleating agent Substances 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 241000237502 Ostreidae Species 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- ALWGNSSDGJLQDG-UHFFFAOYSA-N propan-2-one terephthalic acid Chemical compound CC(=O)C.C(C1=CC=C(C(=O)O)C=C1)(=O)O ALWGNSSDGJLQDG-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种非化学成核型聚酯成核剂的制备方法，该成核剂为对苯二甲酸酯单羧酸碱金属盐，结构式为
本发明成核剂的制备方法是采用两相合成方法，以对苯二甲酸酯为原料，在丙酮溶液中用氢氧化钠水解制成，该方法副反应少，反应完全，得率高，纯度高，反应时间短，其纯度为98%以上，可进行批量生产。
The invention discloses a preparation method of a non-chemical nucleating polyester nucleating agent. The nucleating agent is a terephthalate monocarboxylic acid alkali metal salt, and its structural formula is
The preparation method of the nucleating agent of the present invention adopts a two-phase synthesis method, using terephthalic acid ester as a raw material, and hydrolyzing it with sodium hydroxide in an acetone solution to make it. The method has few side reactions, complete reaction, and high yield. High purity, short reaction time, its purity is over 98%, and can be mass-produced.
Description
The present invention relates to a kind of method for making that has carboxyl to connect the compound on the six-membered aromatic ring carbon atom, specially refer to a kind of method for making of terephthalate monocarboxylic acid an alkali metal salt.
Macromole carboxylate salt nucleator, for example poly-(ethylene-propylene acid sodium-salt) multipolymer and various small molecules carboxylate salt nucleator, all be polyester (PET) engineering plastics nucleators commonly used, the nucleogenesis of this class nucleator is in the PET course of processing and PET carries out chemical reaction, make the PET molecular rupture, meanwhile, connect the carboxylic acid sodium ionic end groups at the PET chain end.And play the PET ionic end groups that is generated just of nucleogenesis, or the ion cluster that forms by ionic end groups.Just because of above-mentioned macromole or micromolecular carboxylic acid sodium salt, after reacting with PET, its reaction product is only just genuine nucleator, so it is " chemical nucleation " mechanism type nucleator [Polymer 27,109 (1986)] that Legras etc. propose above-mentioned this class nucleator, above-mentioned this class " chemical nucleation " nucleator, though nucleation efficient height, but usually cause the PET molecular weight degradation inevitably, thereby infringement mechanical property, particularly erosion-resisting characteristics.
Cause in the prior art that in order to overcome molecular weight degradation provides the efficient nucleator of " non-chemical nucleation type " small molecules metal carboxylate of a kind of " two-phase synthetic method " preparation with the infringement erosion-resisting characteristics.Can in polyester engineering plastic, be used widely.
Small molecules carboxylate salt nucleator provided by the invention, in the course of processing and PET react with not, do not cause PET macromole molecular weight degradation, and very high crystallization nucleation efficient is arranged, consumption has only 0.1～1.2%, can obtain than above-mentioned chemical nucleation type nucleator crystallization rate faster.
The efficient nucleator of " non-chemical nucleation type " small molecules organic carboxyl acid salt that the present invention proposes has following general formula:
This kind nucleator is a kind of terephthalate monocarboxylate that ester appended is arranged in the phenyl ring contraposition, Me=Na wherein, K or Zn; R=CH
3, C
2H
5, C
3H
7
The present invention proposes a kind of " non-chemical nucleation type " carboxylate salt nucleator with brand-new indignant thought of above-mentioned carboxylate structure.Because its " non-chemical nucleation " mechanism therefore in the PET course of processing, does not cause the PET molecular weight degradation.The essence of its " non-chemical nucleation " mechanism is confirmed by FT-IR: after PET powder that purifying is crossed and 20% nucleator of the present invention carried out melt blending, through dissolving repeatedly and precipitating, if nucleator, chemical reaction took place then with whole flush awaies in discord PET.The FTIR spectrogram of sample will be identical with the FTIR spectrogram of pure PET sample.
The preparation method of non-chemical nucleation type nucleator of the present invention is to adopt the two-phase building-up process, and step is carried out in the following order:
The raw material dimethyl terephthalate (DMT) is dissolved in solubility parameters σ at 9.7-9.9 (cal/cm at 35-55 ℃
3)
1/2Solvent in; wherein best in the mixed solvent with acetone or acetone and alcohol; its weight ratio of the latter is 1: 3～1: 6; become transparent homogeneous phase solution after waiting to dissolve; the alcoholic solution that adds sodium hydroxide is more just separated from homogeneous phase solution after one of them ester group is hydrolyzed generation terephthalate monocarboxylate such as single sodium salt immediately, enters the solid phase attitude; thereby protected another ester group, no longer be subjected to the attack of hydrolytic reagent.Reaction equation is as follows:
Described aromatic diacid ester such as dimethyl terephthalate (DMT), diethyl terephthalate or terephthalic acid dipropyl) with the mol ratio of sodium hydroxide be 0.9: 1～1: 1.1, the terephthalic acid monocarboxylate of gained does not need purification process, purity can reach 96-98%, and productive rate can reach more than 90%.
Nucleator of the present invention carries out chemical reaction owing to add the PET that gets along well man-hour at PET, and is therefore little to the PET molecular weight degradation.Table 1 for nucleator of the present invention behind 270 ℃ of melt blendings, the intrinsic viscosity value (η) of PET sample and control sample Sodium Benzoate and PET be the intrinsic viscosity value [η] behind the melt blending under the same conditions
Table 1
Therefore nucleator of the present invention, adds nucleator of the present invention owing to do not cause the PET molecular weight degradation in the course of processing, not only does not cause that the PET erosion-resisting characteristics descends, and significantly increases erosion-resisting characteristics when at the 0.3-0.5% consumption.Nucleator content of the present invention is to the influence of PET impact-resistance.See Table 2.
Table 2 nucleator content (%) notched Izod impact strength (Kg.cm/cm
2)
0 3．5
0．3 6．0
0．5 4．5
1．0 3．5
Nucleator of the present invention has very high nucleating effect, has accelerated the crystallization rate of polyester, and influence sees Table 3 to nucleator content to the PET crystallization rate:
Table 3
The DSC data that add the crystallization property of PET after the nucleator of the present invention see Table 4.
Table 4
Last table data are to measure PET with DSC to add and be warming up to 300 ℃ after 0.5% nucleator and placed 5 minutes, and cooling then is to be Tc at the crystallization peak temperature of temperature-fall period.Sample is warming up to 300 ℃ placed 5 minutes, quenching heats up the sample behind the quenching more then, and the Tc of temperature-rise period is to be Th.The Tc temperature high Th temperature that heals is lower, shows that then the PET crystallization is faster.Peak width at half height/peak height value is littler, represents that also the PET crystallization is faster.Clearly, nucleator of the present invention is compared with Sodium Benzoate, is a kind of more effective PET crystallization nucleating agent.
The preparation method of nucleator of the present invention adopts the two-phase synthetic method, with the terephthalate is raw material, in acetone soln, make with sodium hydroxide or potassium hydroxide hydrolysis, this method side reaction is few, react completely, the yield height, the reaction times is short, its purity is more than the 96-98%, can produce in batches.
Embodiment 1,
Dimethyl terephthalate (DMT) 194 grams are dissolved in 800ml acetone 35-55 ℃ of temperature, 40 gram NaoH are dissolved in the 240ml methyl alcohol.The NaoH-alcoholic solution is added dropwise in transparent terephthalate-acetone soln, and at this moment clear solution becomes oyster white gradually.Reacted completely in about 2 hours, and filtered then, and wash secondary with hot acetone, vacuum-drying is pulverized, and sieves, and promptly obtains white powder, and productive rate 98%, product are through ultimate analysis, and analytical value and theoretical value are close.
Theoretical value C:53.47 H:3.47 analytical value C:53.06 H:3.39
Embodiment 2,
The NaoH-methanol solution is disposed at 20 liter reactors, and jin methyl alcohol placed 20 liter reactors under agitation to add 1.410 kilograms of (35.3mol) NaoH in 8.46 minutes, stirs NaoH is dissolved fully.
In 200 liter reactors, add 90 kilograms in acetone, 16 kilograms of methyl alcohol, under agitation add 6.83 kilograms of (35.2mol) dimethyl terephthalate (DMT), to 44-50 ℃, dimethyl terephthalate (DMT) is dissolved transparent fully with heat temperature raising, drips the above-mentioned NaoH/CH that configures then
3OH solution, after 3-4 minute, the reaction mixture muddiness, keep about 50 ℃ 4 hours, filter then, filter cake is washed once with hot acetone, 80 ℃ of vacuum-dryings are pulverized, packing, product is a white powder, productive rate 96.2%, the ultimate analysis value conforms to theoretical value.
Analytical value C:53.36, H:3.29; Theoretical value C:
Claims (2)
1, a kind of method for making of non-chemical nucleation type polyester nucleator is characterized in that described nucleator is a terephthalate monocarboxylic acid sodium salt, and it is to be undertaken by following sequential steps:
The raw material dimethyl terephthalate (DMT) is dissolved in acetone or the acetone-methanol mixed solvent at 35-55 ℃, becomes transparent homogeneous phase solution after waiting to dissolve, be added dropwise to the alcoholic solution of sodium hydroxide again, generate terephthalate monocarboxylic acid sodium salt.
2, the method for making of a kind of non-chemical nucleation type polyester nucleator according to claim 1, the mol ratio that it is characterized in that described dimethyl terephthalate (DMT) and sodium hydroxide is 0.9: 1～1: 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109004A CN1065857C (en) | 1996-07-19 | 1996-07-19 | Non-chemical nucleation type polyester nucleator and its preparing process and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109004A CN1065857C (en) | 1996-07-19 | 1996-07-19 | Non-chemical nucleation type polyester nucleator and its preparing process and use |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00105988 Division CN1117804C (en) | 2000-04-24 | 2000-04-24 | Application of monocarboxyl terephthalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1167753A CN1167753A (en) | 1997-12-17 |
| CN1065857C true CN1065857C (en) | 2001-05-16 |
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ID=5120145
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109004A Expired - Fee Related CN1065857C (en) | 1996-07-19 | 1996-07-19 | Non-chemical nucleation type polyester nucleator and its preparing process and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1065857C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5025093A (en) * | 1972-12-08 | 1975-03-17 | ||
| JPS617599A (en) * | 1984-06-20 | 1986-01-14 | 松下電工株式会社 | Device for firing discharge lamp |
-
1996
- 1996-07-19 CN CN96109004A patent/CN1065857C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5025093A (en) * | 1972-12-08 | 1975-03-17 | ||
| JPS617599A (en) * | 1984-06-20 | 1986-01-14 | 松下電工株式会社 | Device for firing discharge lamp |
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| Publication number | Publication date |
|---|---|
| CN1167753A (en) | 1997-12-17 |
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