CN102504746A - Method for preparing PET (polyethylene terephthalate) copolyester hot melt adhesive for film preparation - Google Patents
Method for preparing PET (polyethylene terephthalate) copolyester hot melt adhesive for film preparation Download PDFInfo
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- CN102504746A CN102504746A CN2011103905064A CN201110390506A CN102504746A CN 102504746 A CN102504746 A CN 102504746A CN 2011103905064 A CN2011103905064 A CN 2011103905064A CN 201110390506 A CN201110390506 A CN 201110390506A CN 102504746 A CN102504746 A CN 102504746A
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- terephthalic acid
- acid
- melt adhesive
- hot melt
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Abstract
The invention relates to a method for preparing PET (polyethylene terephthalate) copolyester hot melt adhesive for film preparation by high incipient melting point, which mainly includes: firstly, conducting the primary esterification of terephthalic acid and ethylene glycol under the action of tetrabutyl titanate /butylhydroxyoxo stannane catalyst; secondly, adding m-phthalic acid, C3 to C6 glycols into a product of the step 1 for secondary esterification, and then performing decompression co-polycondensation to obtain copolymer; and thirdly, adding polyethylene glycol 400 into a product of the step 2, and softening the copolymer to obtain the PET copolyester hot melt adhesive for film preparation, which is high temperature resistant and not prone to clotting in transport and storage.
Description
Technical field
The present invention relates to a kind of preparation method who makes film with the PET copolyester hot melt adhesive.It is high to the objective of the invention is to hope to obtain a kind of fusing point just, and the system film that when transportation in summer and storage, is difficult for long-pending knot is used the PET copolyester hot melt adhesive.
Background technology
Hot melt adhesive is the heating and melting applying glue, at room temperature solidifies rapidly and realizes bonding caking agent, by not solvent-laden and at room temperature form for the difficult volatility of solid, non-flammable resin.Generally can be divided into ethene and acetate ethylene copolymer class, polyester, polyamide-based etc. according to the composition of hot melt adhesive matrix resin.Wherein, polyester hot-melt adhesive all is superior to other two kinds of hot melt adhesives on thermotolerance, winter hardiness, wet fastness, ageing-resistant and electrical property etc.
At present, it is less relatively to be engaged in the unit of development of high fusing point polyester hot-melt adhesive just and exploitation.From prior art, the first fusing point of the polyester hot-melt adhesive of developing is all lower, thereby hot-melt adhesive powder or the long-pending easily knot of film glue into piece in summer high temperature transportation and when storing.
Summary of the invention
The object of the invention is exactly to provide a kind of adaptation to make the preparation method of film with the PET copolyester hot melt adhesive at the high fusing point (more than 40 ℃) just of transportation under the hot conditions, storage for the defective that overcomes above-mentioned prior art existence, satisfies the needs of association area.
Method of the present invention comprises the steps:
(1) terephthalic acid and terepthaloyl moietie carry out esterification one time under tetrabutyl titanate/butyl stannonic acid catalyst action, and temperature of reaction is 180～200 ℃, and the time is 2.0～2.5 hours;
(2) with m-phthalic acid and PEG 400, C
3～C
6Divalent alcohol adds the product of step (1), carries out the secondary esterification, and temperature is 190～220 ℃; The water that generated of reaction is steamed, when the quantity of distillate of water is 90～95% of a theoretical amount, at 220～250 ℃; 80～130Pa decompression copolycondensation down, the time is 1.5～3.0 hours, obtains multipolymer;
(3) deactivation system vacuum state under 220～250 ℃ and normal pressure, adds the product of step (2) with auxiliary agent, and constant temperature stirred 0.5～1.0 hour, must make film and use the PET copolyester hot melt adhesive;
Said C
3～C
6Divalent alcohol is selected from 1, more than one in ammediol, glycol ether or the pinakon;
Said terephthalic acid, m-phthalic acid, terepthaloyl moietie, C
3～C
6Mol ratio between divalent alcohol and the PEG 400 is respectively:
Terephthalic acid: m-phthalic acid=1.0: 0.3～0.5;
Terephthalic acid: terepthaloyl moietie=1.0: 1.5～2.0;
Terepthaloyl moietie: C
3～C
6Divalent alcohol: PEG 400=1.0: 0.2～0.5: 0.02～0.03.
Said catalyzer is tetrabutyl titanate and butyl stannonic acid, and the mass ratio of the quality of catalyzer and terephthalic acid is respectively:
Tetrabutyl titanate: terephthalic acid=0.15～0.30: 100;
Butyl stannonic acid: terephthalic acid=0.10～0.25: 100.
Described auxiliary agent is a kind of in paraffin, the Microcrystalline Wax, and the quality of its adding is 1.5%～3.0% of a terephthalic acid quality.
Compared with prior art; Innovative point of the present invention is: the copolyester hot melt adhesive that the used technology of the present invention is made has 40 ℃ first fusing point; Its micro-melting range is 40～120 ℃; The stand up to high temperatures test of environment of this type of copolyester hot melt adhesive is difficult for long-pending knot in summer and glues into piece in transportation and the storage process.
Embodiment
Embodiment 1
Have in the polymerization reaction kettle of water distilling apparatus at 2.5L, add terephthalic acid (249.15g), terepthaloyl moietie (183.77g), butyl stannonic acid (0.25g) and tetrabutyl titanate (0.5g), heating, stirring, material begins fusing when interior temperature reaches 148 ℃; In above-mentioned reactant, add m-phthalic acid (83.05g), PEG 400 (30.40g), Diethylene Glycol (80.56g), stir then and heat up, when interior temperature reaches 193 ℃ of left and right sides; Begin to have water to distillate, continue to be warming up to 200 ℃, steam the by product that reaction generates; When overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below the 130Pa; In 2.5 hours reaction times, polycondensation finishes.The deactivation system vacuum state under 225 ℃ and normal pressure, adds the product of step (2) with Microcrystalline Wax (6.20g), and constant temperature stirred 0.5 hour, copolyester hot melt adhesive.At last with the reactant extruding pelletization, behind the freezing and pulverizing for use.
Detect according to standard GB/T4608-84 and GB/T3682-2000 respectively, the fusing point of this product is 41～112 ℃, melts to refer to be 27.2g/min.
Embodiment 2
Have in the polymerization reaction kettle of water distilling apparatus at 2.5L, add terephthalic acid (249.15g), terepthaloyl moietie (222.06g), butyl stannonic acid (0.25g) and tetrabutyl titanate (0.37g), heating, stirring, material begins fusing when interior temperature reaches 178 ℃; In above-mentioned reactant, add m-phthalic acid (83.05g), PEG 400 (30.40g), Diethylene Glycol (97.36g), stir then and heat up, when interior temperature reaches 192 ℃ of left and right sides; Begin to have water to distillate, continue to be warming up to 209 ℃, steam the by product that reaction generates; When overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below the 130Pa; In 3.0 hours reaction times, polycondensation finishes.The deactivation system vacuum state under 240 ℃ and normal pressure, adds the product of step (2) with Microcrystalline Wax (3.33g), and constant temperature stirred 0.5 hour, copolyester hot melt adhesive.At last with the reactant extruding pelletization, behind the freezing and pulverizing for use.
Detect according to standard GB/T4608-84 and GB/T3682-2000 respectively, the fusing point of this product is 42～124 ℃, melts to refer to be 19.7g/min.
Embodiment 3
Have in the polymerization reaction kettle of water distilling apparatus at 2.5L, add terephthalic acid (249.15g), terepthaloyl moietie (164.92g), butyl stannonic acid (0.63g) and tetrabutyl titanate (0.75g), heating, stirring, material begins fusing when interior temperature reaches 175 ℃; In above-mentioned reactant, add m-phthalic acid (83.05g), PEG 400 (44.69g) Diethylene Glycol (72.52g), stir then and heat up, when interior temperature reaches 193 ℃ of left and right sides; Begin to have water to distillate, continue to be warming up to 208 ℃, steam the by product that reaction generates; When overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below the 130Pa; In 3.0 hours reaction times, polycondensation finishes.The deactivation system vacuum state under 240 ℃ and normal pressure, adds the product of step (2) with Microcrystalline Wax (6.20g), and constant temperature stirred 0.5 hour, copolyester hot melt adhesive.At last with the reactant extruding pelletization, behind the freezing and pulverizing for use.
Detect according to standard GB/T4608-84 and GB/T3682-2000 respectively, the fusing point of this product is 42～116 ℃, melts to refer to be 20.6g/min
Embodiment 4
Have in the polymerization reaction kettle of water distilling apparatus at 2.5L, add terephthalic acid (249.15g), terepthaloyl moietie (164.85g), butyl stannonic acid (0.55g) and tetrabutyl titanate (0.5g), heating, stirring, material begins fusing when interior temperature reaches 176 ℃; In above-mentioned reactant, add m-phthalic acid (83.05g), PEG 400 (30.40g), Ucar 35 (23.10g), Diethylene Glycol (80.56g), stir then and heat up, when interior temperature reaches 194 ℃ of left and right sides; Begin to have water to distillate, continue to be warming up to 206 ℃, steam the by product that reaction generates; When overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below the 130Pa; In 3.0 hours reaction times, polycondensation finishes.The deactivation system vacuum state under 240 ℃ and normal pressure, adds the product of step (2) with Microcrystalline Wax (6.57g), and constant temperature stirred 0.5 hour, copolyester hot melt adhesive.At last with the reactant extruding pelletization, behind the freezing and pulverizing for use.
Detect according to standard GB/T4608-84 and GB/T3682-2000 respectively, the fusing point of this product is 44～128 ℃, melts to refer to be 19.2g/min
Embodiment 5
Have in the polymerization reaction kettle of water distilling apparatus at 2.5L, add terephthalic acid (220.91g), terepthaloyl moietie (115.32g), butyl stannonic acid (0.55g) and tetrabutyl titanate (0.5g), heating, stirring, material begins fusing when interior temperature reaches 177 ℃; In above-mentioned reactant, add m-phthalic acid (110.46g), PEG 400 (30.40g), Ucar 35 (24.33g), Diethylene Glycol (56.18g), stir then and heat up, when interior temperature reaches 196 ℃ of left and right sides; Begin to have water to distillate, continue to be warming up to 208 ℃, steam the by product that reaction generates; When overhead product reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below the 130Pa; In 3.0 hours reaction times, polycondensation finishes.The deactivation system vacuum state under 240 ℃ and normal pressure, adds the product of step (2) with Microcrystalline Wax (6.20g), and constant temperature stirred 0.5 hour, copolyester hot melt adhesive.At last with the reactant extruding pelletization, behind the freezing and pulverizing for use.
Detect according to standard GB/T4608-84 and GB/T3682-2000 respectively, the fusing point of this product is 41～114 ℃, melts to refer to be 25.2g/10min.
Claims (3)
1. a preparation method who makes film with the PET copolyester hot melt adhesive is characterized in that comprising the steps:
(1) terephthalic acid and terepthaloyl moietie carry out esterification one time under tetrabutyl titanate/butyl stannonic acid catalyst action, and temperature of reaction is 180～200 ℃, and the time is 2.0～2.5 hours;
(2) with m-phthalic acid and PEG 400, C
3～C
6Divalent alcohol adds the product of step (1), carries out the secondary esterification, and temperature is 190～220 ℃; The water that reaction is generated is steamed; When the quantity of distillate of water be theoretical amount 90～95% the time, be warming up to 220～250 ℃, 80～130Pa decompression copolycondensation down; Time is 1.5～3.0 hours, obtains multipolymer;
(3) deactivation system vacuum state under 220～250 ℃ and normal pressure, adds the product of step (2) with auxiliary agent, and constant temperature stirred 0.5～1.0 hour, must make film and use the PET copolyester hot melt adhesive;
Said C
3～C
6Divalent alcohol is selected from 1, more than one in ammediol, glycol ether or the pinakon;
Said terephthalic acid, m-phthalic acid, terepthaloyl moietie, C
3～C
6Mol ratio between divalent alcohol and the PEG 400 is respectively:
Terephthalic acid: m-phthalic acid=1.0: 0.3～0.5;
Terephthalic acid: terepthaloyl moietie=1.0: 1.5～2.0;
Terepthaloyl moietie: C
3～C
6Divalent alcohol: PEG 400=1.0: 0.2～0.5: 0.02～0.03.
2. method according to claim 1 is characterized in that, said catalyzer is tetrabutyl titanate and butyl stannonic acid, and the mass ratio of the quality of catalyzer and terephthalic acid is respectively:
Tetrabutyl titanate: terephthalic acid=0.15～0.30: 100;
Butyl stannonic acid: terephthalic acid=0.10～0.25: 100.
3. method according to claim 1 is characterized in that, described auxiliary agent is selected from a kind of in paraffin and the Microcrystalline Wax, and the quality of its adding is 1.5%～3.0% of a terephthalic acid quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103905064A CN102504746A (en) | 2011-11-30 | 2011-11-30 | Method for preparing PET (polyethylene terephthalate) copolyester hot melt adhesive for film preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103905064A CN102504746A (en) | 2011-11-30 | 2011-11-30 | Method for preparing PET (polyethylene terephthalate) copolyester hot melt adhesive for film preparation |
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|---|---|
| CN102504746A true CN102504746A (en) | 2012-06-20 |
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ID=46216883
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103905064A Pending CN102504746A (en) | 2011-11-30 | 2011-11-30 | Method for preparing PET (polyethylene terephthalate) copolyester hot melt adhesive for film preparation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421460A (en) * | 2013-07-03 | 2013-12-04 | 上海天洋热熔胶有限公司 | Preparation method of crystalloid and transparent copolyester hot melt adhesive with high melting point |
| CN103725244A (en) * | 2012-10-16 | 2014-04-16 | 上海天洋热熔胶有限公司 | Method for preparing modified terephthalic acid neopentyl glycol copolyester hot melt adhesive for making membranes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2293754C1 (en) * | 2005-10-20 | 2007-02-20 | Общество с ограниченной ответственностью "Полигма" | Composition of the adhesive film material for the laser etching materials |
| CN101735437A (en) * | 2008-11-04 | 2010-06-16 | 中富(广汉)化工实业有限公司 | Copolyester with low melting point and synthesis method thereof |
-
2011
- 2011-11-30 CN CN2011103905064A patent/CN102504746A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2293754C1 (en) * | 2005-10-20 | 2007-02-20 | Общество с ограниченной ответственностью "Полигма" | Composition of the adhesive film material for the laser etching materials |
| CN101735437A (en) * | 2008-11-04 | 2010-06-16 | 中富(广汉)化工实业有限公司 | Copolyester with low melting point and synthesis method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725244A (en) * | 2012-10-16 | 2014-04-16 | 上海天洋热熔胶有限公司 | Method for preparing modified terephthalic acid neopentyl glycol copolyester hot melt adhesive for making membranes |
| CN103725244B (en) * | 2012-10-16 | 2015-02-04 | 上海天洋热熔粘接材料股份有限公司 | Method for preparing modified terephthalic acid neopentyl glycol copolyester hot melt adhesive for making membranes |
| CN103421460A (en) * | 2013-07-03 | 2013-12-04 | 上海天洋热熔胶有限公司 | Preparation method of crystalloid and transparent copolyester hot melt adhesive with high melting point |
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|---|---|---|---|
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| PB01 | Publication | ||
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Application publication date: 20120620 |