CN100430428C - Use of clay mineral as polyester polycondensation catalyst - Google Patents
Use of clay mineral as polyester polycondensation catalyst Download PDFInfo
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- CN100430428C CN100430428C CNB2005100021831A CN200510002183A CN100430428C CN 100430428 C CN100430428 C CN 100430428C CN B2005100021831 A CNB2005100021831 A CN B2005100021831A CN 200510002183 A CN200510002183 A CN 200510002183A CN 100430428 C CN100430428 C CN 100430428C
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- clay mineral
- polycondensation catalyst
- polyester
- polyester polycondensation
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Abstract
The present invention discloses the application of clay minerals used as a polyester polycondensation catalyst. The clay minerals are characterized in that main components comprise SiO2 and Al2O3, the granularity is smaller than 200 meshes, the structure of the clay minerals is of layered or fibriform aluminosilicate mineral powder, and the meltage of the clay minerals in dibasic alcohol at 210 DEG C is higher than 0.10 wt%. The polycondensation catalyst of the present invention belongs to natural minerals, which does not contain heavy metal and has no harm to human beings and animals, and thus, the polycondensation catalyst is a novel polycondensation catalyst conforming to the requirement of environmental protection. The content of carboxyl end groups of polyethylene glycol terephthalate and copolymers thereof prepared according to the present invention is lower than 20 mmol/Kg, and the thermal stability is good.
Description
Technical field
The present invention relates to the purposes of clay mineral as polyester polycondensation catalyst.
Background technology
The method of synthesizing polyester can be divided into two stages usually.Fs is direct esterification reaction or the rudimentary carboxylate (as dimethyl ester) of di-carboxylic acid and the transesterification reaction of dibasic alcohol of di-carboxylic acid and dibasic alcohol, generate the esterification products of di-carboxylic acid and dibasic alcohol, the direct esterification reaction of di-carboxylic acid and dibasic alcohol does not need catalyzer, but use catalyzer can add fast response, transesterification reaction then needs catalyzer; Subordinate phase is that the esterification products of di-carboxylic acid and dibasic alcohol carries out polycondensation under reduced pressure, until generating the high-molecular weight polyester.Polycondensation needs suitable catalyzer, and polycondensation catalyst commonly used at present has the compound of metals such as Sb, Ti, Ge.The Sb series catalysts is respond well, is widely used, and at present about PET more than 90% production is adopted the Sb series catalysts, but Sb is a kind of harmful heavy metal, does not meet environmental requirement, has faced increasing environmental protection pressure in developed country at present; Though Ti series catalysts catalytic activity is very high, side reaction is more, and some organic titanate class catalyzer are very unstable, and therefore facile hydrolysis is deposited strict; And Ge is a kind of rare metal of China, costs an arm and a leg, and it is very high therefore to make the catalyzer cost with Ge.In recent years, developed country just is being devoted to develop some novel polyester polycondensation catalysts, to substitute the traditional catalyst of using at present.
Summary of the invention
The object of the present invention is to provide the purposes of clay mineral as polyester polycondensation catalyst.
Clay mineral of the present invention is: main component is SiO
2And Al
2O
3, granularity is stratiform or fibrous aluminosilicate mineral powder less than 200 orders, structure, the meltage of this clay mineral in 210 ℃ dibasic alcohol is higher than 0.10wt% (with respect to the catalyst themselves dry mass), when being used for production of polyester, this catalyzer can be with dibasic alcohol (as ethylene glycol, 1, ammediol, 1,4-butyleneglycol or 1,4-cyclohexanedimethanol etc.) solution form is added, catalyzer (being dissolved in the dibasic alcohol part) addition is about 10ppm to 5000ppm (with respect to the theoretical yield of polyester), the addition of preferred 50ppm to 3000ppm.Also can add with the pressed powder form, addition is 0.10wt% to 15wt% (with respect to the theoretical yield of polyester), and preferred addition is 0.10wt% to 10wt% (with respect to the theoretical yield of polyester).
Specifically, clay mineral of the present invention mainly comprises the mixture of kaolin, mica, polynite, polygorskite, sepiolite, vermiculite etc. and their arbitrary proportions, the mixture of preferred kaolin, mica, polynite, polygorskite and their arbitrary proportions, more preferably polynite, the most preferably mixture of sodium-based montmorillonite, calcium-base montmorillonite or their arbitrary proportion.The above mineral all can obtain from commercially available channel.
The polycondensation of polycondensation catalyst catalyst, polyester is a kind of homogeneous reaction.It has been generally acknowledged that catalyzer is dissolved in the alcoholate catalysis polycondensation again that forms dibasic alcohol in the reaction medium earlier.Therefore, the meltage of clay mineral catalyzer in dibasic alcohol is high more, and then catalytic activity is high more.Its measuring method of meltage in dibasic alcohol is as follows: dibasic alcohol and sticking scholar's catalyzer mix with 25 to 1 mass ratio; 210 ℃ of backflows; protection of inert gas; stir and use the whizzer centrifugation after 2 hours; weighing after the sediment thorough drying, determine the meltage of catalyzer according to the minimizing of its quality.Because of the production standard of the commercially available clay mineral product of difference different, polyester polycondensation catalyst of the present invention should select for use the meltage in dibasic alcohol to be higher than the clay mineral of 0.10wt% (with respect to exsiccant clay quality), and the preferred dissolution amount is higher than the clay mineral of 0.50wt%.
Described clay mineral in use, particle is more little, its solubleness in dibasic alcohol is high more, then the catalyst activity of unit mass is high more.Therefore, described clay mineral should grind to form the above powder of 200 orders, the powder that preferred 300 orders are above.
The clay mineral catalyzer can add in any time before polycondensation begins.During use, for guaranteeing product quality, can add typical additives, as tinting material, matting agent, the agent of chain cladodification, stablizer or the like, its consumption is identical with ordinary method with usage.
The polyester that the present invention is suitable for can comprise terephthalic acid (dimethyl ester), 2,6-naphthalic acid (dimethyl ester) and ethylene glycol, 1, ammediol, 1,4-butyleneglycol or 1, the polycondensation product of 4-cyclohexanedimethanol or copolycondensation product, it also can be the multipolymer of these di-carboxylic acid (dimethyl ester) and dibasic alcohol and other di-carboxylic acid (dimethyl ester) or dibasic alcohol, these other di-carboxylic acid (dimethyl ester) or dibasic alcohol have m-phthalic acid (dimethyl ester), P-hydroxybenzoic acid, 4,4 '-the xenyl dicarboxylic acid, glycol ether, molecular weight is lower than 2000 polyoxyethylene glycol, molecular weight is lower than 3000 PTMG etc., and preferred polyester is a polyethylene terephthalate.
Polycondensation catalyst of the present invention is a kind of natural mineral, and this catalyzer has and do not contain heavy metal, to person poultry harmless's characteristics, is a kind of polycondensation catalyst of novel compliance with environmental protection requirements.Polyethylene terephthalate and multipolymer thereof by the present invention's preparation are characterised in that content of carboxyl end group is lower than 20mmol/Kg and does not contain heavy metal, and Heat stability is good.
Embodiment
Following embodiment illustrates embodiment of the present invention, and some parameters among the embodiment are measured by the following method.
Intrinsic viscosity (I.V.): the 0.1250g polyester is dissolved in 25ml phenol/sym.-tetrachloroethane (1/1wt) mixed solvent, in 25 ℃ of measurements.
End carboxyl concentration: small amount of polyester is dissolved in the phenylcarbinol, is indicator with the phenolsulfonphthalein, carries out acid base titration with the potassium hydroxide ethylene glycol solution of 0.01N and records.
Embodiment 1
6.0g300 order sodium-based montmorillonite powder is scattered in the 150g ethylene glycol; under 210 ℃ of nitrogen protections, refluxed 2 hours; be cooled to room temperature; use the whizzer centrifugation; the quality of dry after measured back settle solids; the meltage of determining polynite is 3.05wt% (with respect to a polynite dry powder); getting the 75.3g upper strata stillness of night drops in the reactor of logical nitrogen with 100.7g dimethyl terephthalate (DMT) and 0.0100g zinc acetate; be warming up to 200 ℃; after theoretical amount methyl alcohol until 95% is steamed; be warming up to 280 ℃, vacuumize, be lower than under the condition of 200Pa polycondensation at pressure after 1.5 hours; add 0.10 gram triphenyl phosphite; polycondensation is after 1.5 hours again, and reaction finishes, and gained polyester A is the water white transparency shape.Use 0.0300gSb
2O
3Be polycondensation catalyst, with the pure polyester B of identical prepared.Be respectively 255.7 ℃ and 256 ℃ with DSC with 20 ℃/minute determination of heating rate A and the fusing point of B, with 20 ℃ of/minute heat-up rate analyses that get, the result shows that the thermal weight loss starting temperature of this polyester A has improved 12 ℃ than polyester B with TGA; Its I.V. of A and B is respectively 0.66 and 0.63, and end carboxyl concentration is 14mmol/Kg and 22mmol/Kg.
Embodiment 2
3.0g220 order calcium-base montmorillonite powder and 90g dimethyl terephthalate (DMT), 10g2,6-naphthalene diformic acid dimethyl ester and 72g ethylene glycol drop in the reactor of logical nitrogen together, be warming up to 200 ℃, after the theoretical amount methyl alcohol until 95% is steamed, be warming up to 280 ℃, vacuumize, be lower than at pressure that polycondensation added 0.10 gram triphenyl phosphite after 1.5 hours under the condition of 200Pa, polycondensation is after 1.5 hours again, reaction finishes, and gets copolyesters.Is 245.2 ℃ with DSC with its fusing point of determination of heating rate of 20 ℃/minute, a very wide in range peak crystallization occurs at about 177 ℃ on the temperature lowering curve, illustrate that the crystallizing power of multipolymer descends, and is 0.70 through measuring its I.V., and holding carboxyl concentration is 12mmol/Kg.
Embodiment 3
6.0g 400 order kaolin powder are scattered in the 150g ethylene glycol; under 210 ℃ of nitrogen protections, refluxed 2 hours; be cooled to room temperature; use the whizzer centrifugation; the quality of dry after measured back settle solids determines that kaolinic meltage is 2.85wt% (with respect to a kaolin dry powder), gets the 45g upper strata stillness of night, 82g terephthalic acid, 4.4g m-phthalic acid and drops into together in the reactor of logical nitrogen; be warming up to 260 ℃, at 2～2.8Kg/cm
3Pressure under esterification 4 hours, be warming up to 275 ℃ then, vacuumize, be lower than at pressure that polycondensation added 0.10 gram triphenyl phosphite after 1.5 hours under the condition of 200Pa, polycondensation is after 2 hours again, reaction finishes.Product is 243.2 ℃ with DSC with its fusing point of determination of heating rate of 20 ℃/minute, a more wide in range peak crystallization occurs at about 169 ℃ on the temperature lowering curve, illustrate that the crystallizing power of multipolymer descends, and is 0.64 through measuring its I.V., and holding carboxyl concentration is 12mmol/Kg.
Embodiment 4
131.8g bishydroxyethyl terephthalate (BHET), 3.0g400 purpose mica powder and 10g ethylene glycol drop in the reactor respectively, be lower than under the condition of 200Pa polycondensation at 280 ℃, pressure 2 hours, add the 0.10g triphenyl phosphite, polycondensation finishes reaction after 1.5 hours again.The I.V. of this product is 0.65, and its end carboxyl concentration is 11mmol/Kg, is Off-white solid after the crystallization.Measure with 20 ℃/minute cooling rate with DSC, their Tc has improved more than 30 ℃ than pure PET, illustrates that the crystallization velocity of this polyester improves greatly, is 0.59 through measuring its I.V..
Embodiment 5
131.8g BHET, 2.0g300 purpose sodium-based montmorillonite powder, 4.0g400 purpose mica powder and 30g ethylene glycol drop in the reactor respectively, be lower than under the condition of 200Pa polycondensation at 280 ℃, pressure 1.5 hours, add the 0.10g triphenyl phosphite, polycondensation finishes reaction after 1.5 hours again.With 20 ℃ of/minute heat-up rate analyses that get, the result shows that the thermal weight loss starting temperature of this polyester has improved 15 ℃ than pure polyester, demonstrates good thermostability to this material with TGA; Measure with 20 ℃/minute cooling rate with DSC, its Tc has improved more than 30 ℃ than pure PET, illustrates that its crystallization velocity improves greatly.
Embodiment 6
3.0g300 order calcium-base montmorillonite powder and 3.0g 300 order vermiculite powder are scattered in 150g 1; in the 4-butyleneglycol; under 210 ℃ of nitrogen protections, refluxed 2 hours; be cooled to room temperature; use the whizzer centrifugation; the quality of dry after measured back settle solids; the meltage of determining clay is 2.20wt% (with respect to a clay dry powder); getting the 90g upper strata stillness of night drops in the reactor of logical nitrogen with 88.5g dimethyl terephthalate (DMT) and 0.0100g zinc acetate; be warming up to 200 ℃; after theoretical amount methyl alcohol until 95% is steamed, be warming up to 260 ℃, vacuumize; be lower than under the condition of 200Pa polycondensation at pressure after 2 hours; add 0.10 gram triphenyl phosphite, polycondensation is after 2 hours again, and reaction finishes.With 20 ℃/minute determination of heating rate, its fusing point is 223.7 ℃ to the gained polyester with DSC.
Claims (7)
1. the purposes of clay mineral as polyester polycondensation catalyst, described clay mineral is: main component is Al
2O
3And SiO
2, granularity the order number more than 200 orders, structure is stratiform or fibrous aluminosilicate mineral powder, the meltage of this clay mineral in 210 ℃ dibasic alcohol is higher than 0.10wt%.
2. according to the purposes of the clay mineral as polyester polycondensation catalyst of claim 1, described clay mineral is the mixture of kaolin, mica, montmorillonite, slope thread soil, sepiolite, vermiculite or their arbitrary proportions.
3. according to the purposes that mineral are used as polyester polycondensation catalyst that is stained with of claim 2, described clay mineral is the mixture of kaolin, mica, polynite, polygorskite or their arbitrary proportions.
4. according to the purposes of the clay mineral as polyester polycondensation catalyst of claim 3, described clay mineral is polynite.
5. according to the purposes of the clay mineral as polyester polycondensation catalyst of claim 4, described clay mineral is the mixture of sodium-based montmorillonite, calcium-base montmorillonite or their arbitrary proportion.
6. according to the purposes of clay mineral as polyester polycondensation catalyst arbitrary among the claim 1-5, it is characterized in that the meltage of this clay mineral in 210 ℃ dibasic alcohol is higher than 0.50wt%.
7. according to the purposes of clay mineral as polyester polycondensation catalyst arbitrary among the claim 1-5, the order number that it is characterized in that described granularity is more than 300 orders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100021831A CN100430428C (en) | 2005-01-18 | 2005-01-18 | Use of clay mineral as polyester polycondensation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100021831A CN100430428C (en) | 2005-01-18 | 2005-01-18 | Use of clay mineral as polyester polycondensation catalyst |
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|---|---|
| CN1807488A CN1807488A (en) | 2006-07-26 |
| CN100430428C true CN100430428C (en) | 2008-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100021831A Expired - Fee Related CN100430428C (en) | 2005-01-18 | 2005-01-18 | Use of clay mineral as polyester polycondensation catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102627759B (en) * | 2012-03-21 | 2014-01-29 | 东华大学 | Polyester catalyst with attapulgite as carrier, preparation thereof and application thereof |
Citations (7)
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|---|---|---|---|---|
| US4032550A (en) * | 1975-11-26 | 1977-06-28 | Emery Industries, Inc. | Process for the production of esters |
| CN1187506A (en) * | 1997-04-30 | 1998-07-15 | 中国科学院化学研究所 | Poly-butylene terephthalate/laminated nm-silicate composite material and its preparing process |
| CN1220677A (en) * | 1997-03-25 | 1999-06-23 | 东丽株式会社 | Catalyst for producing polyester, process for producing the same, and process for producing polyester by using the same |
| CN1272513A (en) * | 1997-04-23 | 2000-11-08 | 中国科学院化学研究所 | Polyester/laminate silicate nanometer composite material and its preparation method |
| US6649690B2 (en) * | 2001-11-30 | 2003-11-18 | Akzo Nobel N.V. | Method for preparing polymers of glycerol with a saponite catalyst |
| WO2004078825A1 (en) * | 2003-03-07 | 2004-09-16 | Mitsubishi Chemical Corporation | Polyester polymerization catalyst, process for producing the same and process for producing polyester therewith |
| EP1477506A1 (en) * | 2003-05-15 | 2004-11-17 | DuPont Sabanci Polyester Europe B.V. | Polymerization catalyst for preparing polyesters, preparation of polyethylene terephthalate and use of polymerization catalyst |
-
2005
- 2005-01-18 CN CNB2005100021831A patent/CN100430428C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032550A (en) * | 1975-11-26 | 1977-06-28 | Emery Industries, Inc. | Process for the production of esters |
| CN1220677A (en) * | 1997-03-25 | 1999-06-23 | 东丽株式会社 | Catalyst for producing polyester, process for producing the same, and process for producing polyester by using the same |
| CN1272513A (en) * | 1997-04-23 | 2000-11-08 | 中国科学院化学研究所 | Polyester/laminate silicate nanometer composite material and its preparation method |
| CN1187506A (en) * | 1997-04-30 | 1998-07-15 | 中国科学院化学研究所 | Poly-butylene terephthalate/laminated nm-silicate composite material and its preparing process |
| US6649690B2 (en) * | 2001-11-30 | 2003-11-18 | Akzo Nobel N.V. | Method for preparing polymers of glycerol with a saponite catalyst |
| WO2004078825A1 (en) * | 2003-03-07 | 2004-09-16 | Mitsubishi Chemical Corporation | Polyester polymerization catalyst, process for producing the same and process for producing polyester therewith |
| EP1477506A1 (en) * | 2003-05-15 | 2004-11-17 | DuPont Sabanci Polyester Europe B.V. | Polymerization catalyst for preparing polyesters, preparation of polyethylene terephthalate and use of polymerization catalyst |
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| CN1807488A (en) | 2006-07-26 |
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Granted publication date: 20081105 Termination date: 20130118 |