CN102492124A - Alcohol in-situ modified high melt strength polyester capable of being used for carbon dioxide foaming, and preparation method and application thereof - Google Patents
Alcohol in-situ modified high melt strength polyester capable of being used for carbon dioxide foaming, and preparation method and application thereof Download PDFInfo
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- CN102492124A CN102492124A CN2011103579008A CN201110357900A CN102492124A CN 102492124 A CN102492124 A CN 102492124A CN 2011103579008 A CN2011103579008 A CN 2011103579008A CN 201110357900 A CN201110357900 A CN 201110357900A CN 102492124 A CN102492124 A CN 102492124A
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- dicarboxylic acid
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Abstract
The invention provides an alcohol in-situ modified high melt strength polyester capable of being used for carbon dioxide foaming, and a preparation method and application thereof. The high melt strength polyester capable of being used for carbon dioxide foaming is characterized in that aromatic dicarboxylic acid or other derivatives, divalent alcohol and polyfunctional group chain extendor are adopted as raw materials, and are directly subject to esterification, melt and polycondensation, so as to obtain long chain branched polyester. The high melt strength polyester for foaming, provided by the invention, is a foam materiel with light mass, high specific strength, high rigidity, good electric insulativity and excellent properties (such as heat insulation property, acoustic insulation property and the like), and has a wide application range.
Description
Technical field
The present invention relates to a kind ofly can be used to foamable polyesters of making foam materials and preparation method thereof.
Background technology
Polyester has good physics, chemistry and mechanics mechanical property; Be widely used in synthon, biaxially oriented film and pet bottle three big fields; Just begun application and development [Ravindranath the sixties in 20th century as engineering plastics; K.and Mashelkar, R.A.Chem Eng Sci.1986,41:2197].Premium propertiess such as the polyester form material has light weight, specific tenacity is big, rigidity is big, electrical insulating property is good, sound deadener/insulator can be applicable to industries such as food product pack, material of construction, wire insulation, microwave container, refrigerator inner panel, sports equipment, automobile, space industry.But in the continuous foamed process of industriallization fusion, polyester only is being higher than under the temperature of fusing point and could flowing; This moment, melt strength, melt viscosity and the extensional viscosity of polyester were very little, and at high temperature, hydrolysis, pyrolysis and thermooxidative degradation take place polyester easily; Cause molecular weight to reduce; Melt rheological property is variation further, can't support the growth and the typing of foaming, so can not get good cellular material [S.Japon in the normal polyester melt foaming process; Etal.Reclying of Poly (EthyleneTerephathalate) Into Closed-Cell Foams.Polym.Eng.Sci.2000,40 (8): 1942-1952].
Melt strength, melt viscosity and the extensional viscosity that how to improve polyester is an important research project.The principal element that influences polyester fondant intensity, melt viscosity and extensional viscosity is the molecular weight of polyester, MWD and long chain branching degree; So must carry out modification to polyester; In the hope of improving the molecular weight of polyester; Widen MWD; Increase long chain branching degree [R.Dhavalikar, etal.Parameters Affecting the Chain Extension and Branching of PET in the Melt State by Polyepoxides.Journal of Applied Polymer Science.2003,87:643-652].
At present mainly be to adopt reaction extrusion molding or blending method to prepare the high polyester that melts intensity, improve the molecular weight of polyester through blend/chain extension/branching reaction.S.Japon; Etal.Reactive processing of Poly (Ethylene Terephathalate) modified with multifunctional epoxy-based additives.Polymer.2000; 41:5809-5818 selects 4,4 ' one MDA four glycidyl group epoxy resin (TGDDM) modified PET, and Z-average molecular weight has increased by 8 times after the modification; Limiting viscosity increases up to 1.13dL/g, and effect is obvious.US5696176 mixes polyolefine and chainextender and obtains the homogeneous phase melt on Branbury mixer; And then the mixture of adding polyester and crystallization nucleating agent; Reaction obtains modified poly ester, and the molecular weight of polyester increases, and MWD broadens; Complex viscosity and Young's modulus increase, and melt strength rises.With polyester and the ethylene copolymer blend that contains carboxyl or ester group or hydroxyl solid phase polycondensation then, the polyester fondant intensity and the melt viscosity that obtain all will be higher than pure polyester among the US5482977.Adopt two-step approach among the US5422381 of M&G company, successfully prepared the foamable polyesters that limiting viscosity surpasses 1.1dL/g.The first step is to extrude mix stages, and polymeric additive is mixed with the polyester fusion mutually; Second step was the solid state condensation stage.The main drawback of this method is that energy consumption is big, and the reaction times is longer.
One Chinese patent application number: 200810125083.1 extrude the uniform mixture of aromatic polyester resins and polyolefine and polyfunctional compound (being selected from the dianhydride and the polyepoxy compound of tetracarboxylic acid aromatic hydrocarbons and/or aromatic carboxylic acid) and to obtain concentrate composition under 160-200 ℃ temperature, are that the regenerate grade polyester resin of 0.5-1.0dL/g mixes in foaming is extruded with concentrate composition and obtains the aromatic polyester resins goods with limiting viscosity again.One Chinese patent application number: 200410041208.4 filter polyester waste material (being mainly polyethylene terephthalate or polybutylene terephthalate) then in reaction kettle for reaction with glycol ether, catalyzer (manganese oxide or zinc acetate or antimonous oxide) and stopper (Resorcinol or Resorcinol) and to obtain the expanded polyester that hard bubbles.One Chinese patent application number: 02802629.2 is that (methyl) acrylic ester polymer or polymkeric substance and the filler (mainly being talcum, lime carbonate, mica, wollastonite, clay or spun glass) of 0.65-1.7dL/g mixes and obtain expandable polyester resin composition with vibrin and synthetic limiting viscosity voluntarily.One Chinese patent application number: 96195115.X obtains the branching foamable polyesters with the reaction of vibrin ethylene copolymer, ethylene copolymer contain that ethene constitutes be selected from the repeating unit that vinylformic acid, methylacrylic acid, alkyl acrylate, alkyl methacrylate and vinyl alcohol monomer constitute.Branched polyester can be processed low-density moulded products, film and sheet material with whipping agent.
No matter be reaction extrude or blend method to prepare the technological process of high fondant-strength melting expanded polyester consuming time longer, and equipment is had special requirement, be not that ten minutes is desirable from technology and economic angle.
Summary of the invention
The object of the present invention is to provide a kind of high fondant-strength polyester that can be used for foaming, overcoming the above-mentioned defective that prior art exists.
The described high fondant-strength polyester that can be used for foaming is to comprise that aromatic dicarboxylic acid or derivatives thereof, divalent alcohol and polyfunctional group chainextender are raw material, the long chain branching polyester that the direct esterification melt polycondensation reaction obtains in the presence of catalyzer;
The parts by weight of aromatic dicarboxylic acid or derivatives thereof, divalent alcohol, polyfunctional group chainextender and catalyzer are:
Preferably, comprise that also parts by weight are 1～5 part stablizer phosphorus compound various commonly used;
The limiting viscosity of described polyester is 0.80-1.5dL/g; Melting index is 1.0～10.0g/10min; Extruding rate of expansion is 2.0～4.0, shows good non-Newtonian fluid behavior, and the melt strength of polyester, melt viscosity and extensional viscosity are very big; Can be used for melt foaming, effect is very good.
Described aromatic dicarboxylic acid and ester derivative thereof are selected from terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate or diethyl terephthalate, phthalic acid or dimethyl phthalate or diethyl phthalate, m-phthalic acid or dimethyl isophthalate or dimethyl isophthalate, methyl terephthalic acid or methyl DMT. Dimethyl p-benzenedicarboxylate or methyl diethyl terephthalate, naphthalene diacid or naphthalene two dimethyl phthalates or naphthalene two diethyl phthalates, biphenyl dicarboxylic acid or biphenyl dicarboxylic acid dimethyl ester or biphenyl dicarboxylic acid diethyl ester.
Preferably terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate;
Described divalent alcohol is selected from the saturated and unsaturated divalent alcohol that the carbon atom number is 2-30, preferably more than one in terepthaloyl moietie, Ucar 35, butyleneglycol or the pentanediol etc.;
Said polyfunctional group chainextender is selected from polyvalent alcohol;
Said polyvalent alcohol is selected from more than one in USP Kosher, hydroxyl trimethylammonium ethane, hydroxyl trimethyl propane or the tetramethylolmethane;
Said catalyzer is Antimony Trioxide: 99.5Min, antimony glycol or iso-butyl titanate etc.;
Preferably, aromatic dicarboxylic acid is terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate, and divalent alcohol is a terepthaloyl moietie, and chainextender is tetramethylolmethane or USP Kosher;
Preferably, said phosphorus compound is the organic or inorganics of trivalent or pentavalent, and phosphoric acid, trimethyl phosphite 99 or triphenylphosphate are preferably arranged, and can be the trivalent of commercially available phosphorus system or the inhibitor of pentavalent, like commercially available PEP36, AP1500, AX-71 etc.
The preparation method of the high fondant-strength polyester that is used to foam of the present invention comprises the steps:
With aromatic dicarboxylic acid or derivatives thereof, divalent alcohol, polyfunctional group chainextender and catalyzer; In inert atmosphere such as nitrogen; 200-250 ℃, gauge pressure is to carry out esterification under the condition of 0-0.5MPa, discharges the water that reaction generates simultaneously; Reacting to water outlet and finish, is that 210-260 ℃, pressure are 10 in temperature then
3-10
4Under the condition of Pa, continue precondensation and carry out the long chain branching reaction simultaneously, the reaction times is 1～3 hour; And then be that 270-300 ℃, pressure are to carry out final minification under the condition of 50-100Pa to gather reaction in temperature; Be 1～3 hour, can obtain the high fondant-strength polyester that is used to foam, limiting viscosity is 0.80-1.5dL/g; Melting index is 1.0～10.0g/10min; Extrude rate of expansion greater than 2, show good non-Newtonian fluid behavior, melt strength, melt viscosity and stretching are sticking very big than the conventional polyester degree.
The parts by weight of aromatic dicarboxylic acid or derivatives thereof, divalent alcohol, polyfunctional group chainextender and catalyzer are:
In the reaction system, can add parts by weight and be 1～5 part stablizer phosphorus compound various commonly used;
The high fondant-strength polyester that is used to foam that the present invention obtains not only can use through various ordinary methods; And it is continuous foamed to be used for the industriallization fusion; Can be used for the preparation engineering foam board, food product pack, material of construction, wire insulation, microwave container, refrigerator inner panel, sports equipment, automotive material, space industry material etc.
The high fondant-strength polyester that is used to foam that the present invention obtains, for a kind of light weight, the foam materials of excellent propertys such as specific tenacity is big, rigidity is big, electrical insulating property is good, sound deadener/insulator, of many uses.
Embodiment
Terephthalic acid (PTA): Shanghai Petrochemial Co Ltd, China Petrochemical Corp provides, and fibre-grade, molecular weight are 166.13g/mol, and fusing point is 300 ℃.
Terepthaloyl moietie (EG): Shanghai Ling Feng chemical reagent ltd produces, and CP, molecular weight are 62.07g/mol, and boiling point is 198 ℃.
Tetramethylolmethane (PENTA): traditional Chinese medicines chemical reagent ltd produces, and CP, molecular weight are 136.15g/mol, and fusing point is 300 ℃.
USP Kosher: Shanghai Ling Feng chemical reagent ltd produces, and CP, molecular weight are 92.09g/mol, and boiling point is 290 ℃.
Antimony glycol (sb2 (EG) 3): Shanghai Petrochemial Co Ltd, China Petrochemical Corp provides, technical grade.
Embodiment 1
In having the 2L pet reaction still of rectifying tower, the mixture of 750g terephthalic acid, 363.11g terepthaloyl moietie, 0.94g tetramethylolmethane and 0.2355g antimony glycol is joined in the reaction kettle, feed nitrogen; Elevated temperature, at 230 ℃, pressure is to carry out esterification under the condition of 0.3MPa; React to the water outlet end, elevated temperature is taken out rough vacuum then; At 250 ℃, 10
41 hour precondensation of reaction again at 280 ℃, under the condition of 50Pa, was reacted 3 hours under the condition of Ppa, and final minification gathers reaction, fed nitrogen at last and removed vacuum, was discharged to slivering sampling in the frozen water.
Embodiment 2
With the device of embodiment 1, the mixture of 750g terephthalic acid, 363.11g terepthaloyl moietie, 5.46g USP Kosher and 0.2355g antimony glycol is joined in the reaction kettle, feed nitrogen; Elevated temperature at 230 ℃, reacts under the condition of gauge pressure 0.3MPa to water outlet and finishes; The pressurization esterification finishes, and elevated temperature is taken out rough vacuum then; At 250 ℃, 10
4Precondensation is 1 hour under the condition of Pa, pumping high vacuum again, and at 280 ℃, final minification gathers reaction 3 hours under the condition of 50Pa, feeds nitrogen at last and removes vacuum, is discharged to slivering sampling in the frozen water.
Embodiment 3
In 80L pet reaction still, the mixture of 37kg terephthalic acid, 18kg terepthaloyl moietie, 60.76g tetramethylolmethane and 13g antimony glycol is joined in the reaction kettle, feed nitrogen; Elevated temperature at 230 ℃, reacts under the condition of gauge pressure 0.3MPa to water outlet and finishes; Elevated temperature then; Take out rough vacuum, at 250 ℃, 10
4Precondensation is 1 hour under the condition of Pa, pumping high vacuum again, and at 280 ℃, final minification gathers reaction 3 hours under the condition of 50Pa, feeds nitrogen at last and removes vacuum, is discharged to slivering sampling in the frozen water.
Comparative Examples 1
With device and the addition of embodiment 1 or embodiment 2, process is also identical, does not add tetramethylolmethane and USP Kosher.
Embodiment 4
Foaming:
The melt foaming experiment is carried out in the supercritical, high pressure still, and the polyester batten is put into autoclave, with the autoclave sealing, puts into the oil bath of design temperature again.Use earlier low pressure CO
2Purge autoclave three times, in autoclave, feed a certain amount of CO then
2, make sample fusion and saturated appropriate time under the temperature and pressure of setting, make CO
2Diffusion reaches balance in the molten polyester.Open pressure relief valve then fast and discharge the CO in the autoclave
2Gas causes bubble nucleating, opens kettle cover, in still, injects frozen water, and cooling foaming sample makes its fixedly moulding, takes out sample analysis then and characterizes.
Evaluation method:
Limiting viscosity (IV): adopt the test of polyester national standard method: GB/T-14190-1993 tests.
Melting index (MFI): adopt the ASTM1238 standard to test.
Extrude rate of expansion: DS=D/D
0, D is the maximum diameter of extrudate, D
0Diameter for nib.
Abscess characterizes: with the polyester batten brittle failure in liquid nitrogen behind the melt foaming, and then surperficial metal spraying, with JSM-6360LV type sem observation surface topography.The density (ρ f) of foaming sample obtains through the balance of being furnished with the density assembly that MettlerToledo company provides, and testing standard is ASTM 792-00.The volume expansion ratio (Rv) of foaming sample is defined as the density (ρ p) of the sample that do not foam and density (ρ f) ratio of foaming back sample: R
v=ρ
p/ ρ
f
Claims (15)
1. can be used for CO
2The high fondant-strength polyester of foaming is characterized in that, is to comprise that aromatic dicarboxylic acid or derivatives thereof, divalent alcohol and polyfunctional group chainextender are raw material, the long chain branching polyester that the direct esterification melt polycondensation reaction obtains in the presence of catalyzer.
2. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that the limiting viscosity of described polyester is 0.80-1.5dL/g, and melting index is 1.0～10.0g/10min, and extruding rate of expansion is 2.0～4.0.
3. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming; It is characterized in that; Described aromatic dicarboxylic acid or its ester derivative are selected from terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate or diethyl terephthalate, phthalic acid or dimethyl phthalate or diethyl phthalate, m-phthalic acid or dimethyl isophthalate or dimethyl isophthalate, methyl terephthalic acid or methyl DMT. Dimethyl p-benzenedicarboxylate or methyl diethyl terephthalate, naphthalene diacid or naphthalene two dimethyl phthalates or naphthalene two diethyl phthalates, biphenyl dicarboxylic acid or biphenyl dicarboxylic acid dimethyl ester or biphenyl dicarboxylic acid diethyl ester.
4. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that described aromatic dicarboxylic acid is a terephthalic acid, and described aromatic dicarboxylic acid verivate is DMT. Dimethyl p-benzenedicarboxylate or diethyl terephthalate.
5. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that described divalent alcohol is selected from the saturated and unsaturated divalent alcohol that the carbon atom number is 2-30.
6. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that described divalent alcohol is more than one in terepthaloyl moietie, Ucar 35, butyleneglycol or the pentanediol.
7. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that said polyfunctional group chainextender is selected from polyvalent alcohol.
8. the CO that can be used for according to claim 7
2The high fondant-strength polyester of foaming is characterized in that said polyvalent alcohol is selected from more than one in USP Kosher, hydroxyl trimethylammonium ethane, hydroxyl trimethyl propane or the tetramethylolmethane.
9. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that said catalyzer is Antimony Trioxide: 99.5Min, antimony glycol or iso-butyl titanate.
10. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that aromatic dicarboxylic acid is terephthalic acid or DMT. Dimethyl p-benzenedicarboxylate, and divalent alcohol is a terepthaloyl moietie, and chainextender is a tetramethylolmethane.
11. the CO that can be used for according to claim 1
2The high fondant-strength polyester of foaming is characterized in that used raw material comprises that also parts by weight are 1～5 part stablizer phosphorus compound.
12. according to each described CO that can be used for of claim 1～10
2The high fondant-strength polyester of foaming is characterized in that the parts by weight of aromatic dicarboxylic acid or derivatives thereof, divalent alcohol, polyfunctional group chainextender and catalyzer are:
13. according to each described CO that can be used for of claim 1～12
2The preparation method of the high fondant-strength polyester of foaming is characterized in that, comprises the steps: aromatic dicarboxylic acid or derivatives thereof, divalent alcohol, polyfunctional group chainextender and catalyzer; In inert atmosphere such as nitrogen; 200-250 ℃, gauge pressure is to carry out esterification under the condition of 0-0.5MPa, discharges the water that reaction generates simultaneously; Reacting to water outlet and finish, is that 210-260 ℃, pressure are 10 in temperature then
3-10
4Under the condition of Pa, continue precondensation and carry out the long chain branching reaction simultaneously, the reaction times is 1～3 hour, and then is that 270-300 ℃, pressure are to carry out final minification under the condition of 50-100Pa to gather reaction in temperature, is 1～3 hour, can obtain being used for CO
2The high fondant-strength polyester of foaming.
14. method according to claim 13 is characterized in that, the parts by weight of aromatic dicarboxylic acid or derivatives thereof, divalent alcohol, polyfunctional group chainextender and catalyzer are:
15. according to each described CO that can be used for of claim 1～12
2The application of the high fondant-strength polyester of foaming is characterized in that, is used for the preparation engineering foam board, food product pack, material of construction, wire insulation, microwave container, refrigerator inner panel, sports equipment, automotive material or space industry material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103579008A CN102492124A (en) | 2011-11-11 | 2011-11-11 | Alcohol in-situ modified high melt strength polyester capable of being used for carbon dioxide foaming, and preparation method and application thereof |
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|---|---|---|---|
| CN2011103579008A CN102492124A (en) | 2011-11-11 | 2011-11-11 | Alcohol in-situ modified high melt strength polyester capable of being used for carbon dioxide foaming, and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492123A (en) * | 2011-11-11 | 2012-06-13 | 华东理工大学 | Method for preparing polyester with high melt strength for foaming CO2 by polyprotic acid in-situ modification and application thereof |
| CN105038146A (en) * | 2015-06-29 | 2015-11-11 | 华东理工大学 | Method for preparing low melt strength polyester / clay nanocomposites for CO2 foam |
| CN106220835A (en) * | 2016-08-16 | 2016-12-14 | 哈尔滨工业大学无锡新材料研究院 | Low terminal carboxy content polyester of organic amine end-blocking and preparation method thereof |
| CN107189043A (en) * | 2017-05-22 | 2017-09-22 | 浙江大学 | Weak crystalline polyester of HMW and its preparation method and application |
| CN109721714A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method that in-situ polymerization prepares high fondant-strength expanded polyester PET |
| CN113150256A (en) * | 2021-04-21 | 2021-07-23 | 浙江恒澜科技有限公司 | Branched copolyester for bead foaming and preparation method thereof |
| CN115216050A (en) * | 2022-07-28 | 2022-10-21 | 上海华峰新材料研发科技有限公司 | Polyester foaming material and preparation method and application thereof |
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| CN102295761A (en) * | 2011-07-11 | 2011-12-28 | 华润包装材料有限公司 | Method for preparing polyester for foaming |
| CN102492123A (en) * | 2011-11-11 | 2012-06-13 | 华东理工大学 | Method for preparing polyester with high melt strength for foaming CO2 by polyprotic acid in-situ modification and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102295761A (en) * | 2011-07-11 | 2011-12-28 | 华润包装材料有限公司 | Method for preparing polyester for foaming |
| CN102492123A (en) * | 2011-11-11 | 2012-06-13 | 华东理工大学 | Method for preparing polyester with high melt strength for foaming CO2 by polyprotic acid in-situ modification and application thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492123A (en) * | 2011-11-11 | 2012-06-13 | 华东理工大学 | Method for preparing polyester with high melt strength for foaming CO2 by polyprotic acid in-situ modification and application thereof |
| CN105038146A (en) * | 2015-06-29 | 2015-11-11 | 华东理工大学 | Method for preparing low melt strength polyester / clay nanocomposites for CO2 foam |
| CN106220835A (en) * | 2016-08-16 | 2016-12-14 | 哈尔滨工业大学无锡新材料研究院 | Low terminal carboxy content polyester of organic amine end-blocking and preparation method thereof |
| CN106220835B (en) * | 2016-08-16 | 2018-05-15 | 哈尔滨工业大学无锡新材料研究院 | Low terminal carboxy content polyester of organic amine end-blocking and preparation method thereof |
| CN107189043A (en) * | 2017-05-22 | 2017-09-22 | 浙江大学 | Weak crystalline polyester of HMW and its preparation method and application |
| CN109721714A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method that in-situ polymerization prepares high fondant-strength expanded polyester PET |
| CN113150256A (en) * | 2021-04-21 | 2021-07-23 | 浙江恒澜科技有限公司 | Branched copolyester for bead foaming and preparation method thereof |
| CN113150256B (en) * | 2021-04-21 | 2022-08-26 | 浙江恒逸石化研究院有限公司 | Branched copolyester for bead foaming and preparation method thereof |
| CN115216050A (en) * | 2022-07-28 | 2022-10-21 | 上海华峰新材料研发科技有限公司 | Polyester foaming material and preparation method and application thereof |
| CN115216050B (en) * | 2022-07-28 | 2023-09-05 | 上海华峰新材料研发科技有限公司 | Polyester foaming material and preparation method and application thereof |
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Application publication date: 20120613 |