CN101245230A - Method for manufacturing linear copolyester hot melt adhesive - Google Patents
Method for manufacturing linear copolyester hot melt adhesive Download PDFInfo
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- CN101245230A CN101245230A CNA2008100337541A CN200810033754A CN101245230A CN 101245230 A CN101245230 A CN 101245230A CN A2008100337541 A CNA2008100337541 A CN A2008100337541A CN 200810033754 A CN200810033754 A CN 200810033754A CN 101245230 A CN101245230 A CN 101245230A
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- hot melt
- dibasic alcohol
- dimethyl terephthalate
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Abstract
The invention provides a method for preparing linear copolyester hot melt rubber, which includes the following steps: (1) dimethyl terephthalate and diol are done with transesterification reaction under the effect of catalyst; (2) aliphatic series dibasic carboxylic acid and stabilizer are added into the product of step (1), obtaining copolymer by decompression and copolycondensation, and obtaining the hot melt rubber. The method for preparing the linear copolyester hot melt rubber adopts linear symmetrical dibasic carboxylic acid as raw material, and the linear copolyester hot melt rubber obtained with diol is characterized by being strong in adhesive strength, fast in crystallization speed, and resistant in water washing and dry washing, and is especially suitable for preparing the corresponding glue film or two sided rubber net interface product.
Description
Technical field
The present invention relates to the preparation method of copolyester hot melt adhesive.
Background technology
Present known polyester hot-melt adhesive all adopts diester and di-carboxylic acid and dibasic alcohol successively after transesterify, esterification, obtains through the decompression polycondensation again.As having disclosed a kind of preparation method of copolyester with low melting point hot melt adhesive among the U.S. Pat P 6255443, Chinese patent CN 1340585 proposes a kind of high-melting-point copolyester hot melt adhesive synthetic technology.Chinese patent 200710043238.2 carries out modification by metal-salt and a kind of ethylene/acrylic acid copolymer of Sorbic Acid to copolyesters, obtains a kind of polyester hot-melt adhesive of better performances.
But from prior art, the copolyester with low melting point hot melt adhesive of being produced, the raw material that in preparation process, has all added the nonlinear molecule structure, as m-phthalic acid, and break copolyesters molecule linear structure thus and tie, reduce the degree of crystallinity and the fusing point of copolyesters, to adapt to the needed requirement of every profession and trade such as clothes.On the other hand, because crystallization rate is slow, its curing speed is also slow, and this will cause the sticking back of the body phenomenon in the lining cloth course of processing, therefore, the gained hot melt adhesive is not suitable for to finish fast on the agglutinating production line at needs to be used, and can not be used to prepare corresponding glued membrane or double faced adhesive tape nethike embrane product.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of linear copolyester hot melt adhesive to overcome the above-mentioned defective that prior art exists, satisfies the needs in relevant field.
Method of the present invention comprises the steps:
(1) with dimethyl terephthalate (DMT) and dibasic alcohol under catalyst action, carry out transesterification reaction under protection of inert gas, temperature of reaction is 150～225 ℃, steams the methyl alcohol that is generated simultaneously, when the methyl alcohol quantity of distillate be theoretical amount 90～95% the time, transesterification reaction finishes;
The mol ratio of dimethyl terephthalate (DMT) and dibasic alcohol is 1: 1.0～1.7, be preferably 1: 1.1～and 1.3;
Said catalyzer is selected from tetraethyl titanate, titanium isopropylate or tetrabutyl titanate, and the molar weight of used catalyzer is 0.01%～0.05% of a dimethyl terephthalate (DMT);
Said dibasic alcohol is selected from 1, the mixture that 4-butyleneglycol and one or more other dibasic alcohol are formed, and said other dibasic alcohol is selected from ethylene glycol, 1, ammediol, 1,6-hexylene glycol or glycol ether etc., 1, the mol ratio of 4-butyleneglycol and other dibasic alcohol is 1: 0.2～1.0;
(2) aliphatic dicarboxylic acid and stablizer are added the product of step (1), carry out esterification, temperature is 190～220 ℃, get rid of the water that reaction generates simultaneously, when the quantity of distillate of water be theoretical amount 90～95% the time, at 220～240 ℃, 90～133Pa decompression copolycondensation down, time is 2.5～5.5 hours, obtains multipolymer;
The mol ratio of aliphatic dicarboxylic acid and dibasic alcohol is 1: 1.0～1.8, be preferably 1: 1.2～and 1.4;
Dimethyl terephthalate (DMT) and aliphatic dicarboxylic acid's mol ratio is 1: 0.2～1.0; Be preferably 0.6～0.8.
Select oneself in diacid, nonane diacid, sebacic acid, undecandioic acid or 12 diacid one or more of said aliphatic dicarboxylic acid;
Said stablizer is selected from trimethyl phosphite 99 or triphenyl phosphite, stabilizing agent dosage be step (2) product weight 0.02%～0.06%;
Compared with prior art, the present invention has following positively effect:
The present invention adopts the ester exchange offspring of rutgers and dibasic alcohol and aliphatic dicarboxylic acid to carry out esterification, obtain linear copolyester hot melt adhesive, this product has shorter, curing speed of open hour characteristics faster, special suitable corresponding glued membrane of preparation or double faced adhesive tape nethike embrane product.
Embodiment
Embodiment 1
Have in the polymerization reaction kettle of water distilling apparatus at 2.0L, add dimethyl terephthalate (DMT) (333g), 1,4-butyleneglycol (200g), ethylene glycol (15g), catalyzer metatitanic acid four butyl esters (0.50g), heating, material melting when interior temperature reaches 150 ℃ begins to stir then; When being warmed up to 152 ℃ of left and right sides, begin to distillate methyl alcohol, temperature reaches 190 ℃ in continuing to be warming up to, and treats that distilled methyl alcohol reaches 90% o'clock of theoretical amount, and transesterification reaction finishes.
In above-mentioned reactant, add sebacic acid (206g), nonane diacid (38.4g), 12 diacid (50g), 1,4-butyleneglycol (117g), 1, ammediol (22.8g), ethylene glycol (18.6g), and add stablizer triphenyl phosphite (0.25g), stir then and heat up, when interior temperature rise to the 192 ℃ left and right sides, begin to have water to distillate, continue to be warming up to 200 ℃, the quantity of distillate of water reach theoretical value 91% after, continue to heat up, when interior temperature reaches 230 ℃, further to steam oligopolymer and the unnecessary alcohol that reaction generates, when overhead product reduces or be slack-off, the high vacuum reaction is carried out in decompression, system pressure remains on below the 100Pa, and in 5.0 hours reaction times, polycondensation finishes.Under nitrogen protection, the deactivation system vacuum state, particle is cut in discharging.
Detect according to standard GB/T4608-84, GB/T3682-2000 and ministerial standard HG/T3716 respectively, the fusing point of this product is 128～133 ℃, melts to refer to be that 19.5g/10min, open hour are 1.3min.
Embodiment 2
In having the polymerization reaction kettle of water distilling apparatus, 2.0L adds dimethyl terephthalate (DMT) (333g), and 1,4-butyleneglycol (220g), glycol ether (40g), catalyzer metatitanic acid four isopropyl esters (0.48g), heating, material melting when interior temperature reaches 150 ℃ begins to stir then; When being warmed up to 152 ℃ of left and right sides, begin to distillate methyl alcohol, temperature reaches 205 ℃ in continuing to be warming up to, and treats that distilled methyl alcohol reaches 92% o'clock of theoretical amount, and transesterification reaction finishes.
In above-mentioned reactant, add sebacic acid (103g), hexanodioic acid (120g), nonane diacid (19.2g), 12 diacid (93.6g), 1,4-butyleneglycol (160g), 1, ammediol (20g), 1,3-hexylene glycol
(23.6g), and add stablizer triphenyl phosphite (0.25g), stir then and heat up, when interior temperature rise to the 180 ℃ left and right sides, begin to have water to distillate, continue to be warming up to 205 ℃, the quantity of distillate of water reach theoretical value 92% after, continue to heat up, when interior temperature reaches 240 ℃, further to steam oligopolymer and the unnecessary alcohol 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.Under nitrogen protection, the deactivation system vacuum state, particle is cut in discharging.
Detect according to standard GB/T4608-84, GB/T3682-2000 and ministerial standard HG/T3716 respectively, the fusing point of this product is 120～128 ℃, melts to refer to be that 22.5g/10min, open hour are 1.8min.
Embodiment 3
In having the polymerization reaction kettle of water distilling apparatus, 2.0L adds dimethyl terephthalate (DMT) (333g), and 1,4-butyleneglycol (220g), 1, ammediol (38g), catalyzer metatitanic acid tetra-ethyl ester (0.40g), heating, material melting when interior temperature reaches 150 ℃ begins to stir then; When being warmed up to 152 ℃ of left and right sides, begin to distillate methyl alcohol, temperature reaches 198 ℃ in continuing to be warming up to, and treats that distilled methyl alcohol reaches 93% o'clock of theoretical amount, and transesterification reaction finishes.
In above-mentioned reactant, add sebacic acid (164.8g), hexanodioic acid (75g), nonane diacid (19.2g), 12 diacid (70.2g), 1,4-butyleneglycol (150g), 1, ammediol (30g), 1,3-hexylene glycol (35.4g), and add stablizer triphenyl phosphite (0.25g), stir then and heat up, when interior temperature rise to the 198 ℃ left and right sides, begin to have water to distillate, continue to be warming up to 220 ℃, the quantity of distillate of water reach theoretical value 95% after, continue to heat up, when interior temperature reaches 240 ℃, further to steam oligopolymer and the unnecessary alcohol that reaction generates, when overhead product reduces or be slack-off, the high vacuum reaction is carried out in decompression, system pressure remains on below the 120Pa, and in 5.0 hours reaction times, polycondensation finishes.Under nitrogen protection, the deactivation system vacuum state, particle is cut in discharging.
Detect according to standard GB/T4608-84, GB/T3682-2000 and ministerial standard HG/T3716 respectively, the fusing point of this product is 120～128 ℃, melts to refer to be that 21.5g/10min, open hour are 1.5min.
Embodiment 4
In having the polymerization reaction kettle of water distilling apparatus, 2.0L adds dimethyl terephthalate (DMT) (333g), and 1,4-butyleneglycol (220g), 1,6-hexylene glycol (70.8g), catalyzer metatitanic acid tetra-ethyl ester (0.30g), heating, material melting when interior temperature reaches 150 ℃ begins to stir then; When being warmed up to 152 ℃ of left and right sides, begin to distillate methyl alcohol, temperature reaches 220 ℃ in continuing to be warming up to, and treats that distilled methyl alcohol reaches 92% o'clock of theoretical amount, and transesterification reaction finishes.
In above-mentioned reactant, add sebacic acid (164.8g), hexanodioic acid (120g), nonane diacid (22.2g), 12 diacid (80g), 1,4-butyleneglycol (160g), 1, ammediol (30g), 1,6-hexylene glycol (35.4
G), and add stablizer triphenyl phosphite (0.25g), stir then and heat up, when interior temperature rise to the 180 ℃ left and right sides, begin to have water to distillate, continue to be warming up to 212 ℃, the quantity of distillate of water reach theoretical value 93% after, continue to heat up, when interior temperature reaches 240 ℃, further to steam oligopolymer and the unnecessary alcohol 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 5.0 hours reaction times, polycondensation finishes.Under nitrogen protection, the deactivation system vacuum state, particle is cut in discharging.
Detect according to standard GB/T4608-84, GB/T3682-2000 and ministerial standard HG/T3716 respectively, the fusing point of this product is 128～132 ℃, melts to refer to be that 23.5g/10min, open hour are 1.9min.
Claims (8)
1. the preparation method of linear copolyester hot melt adhesive is characterized in that, comprises the steps:
(1) with dimethyl terephthalate (DMT) and dibasic alcohol under catalyst action, under protection of inert gas, carry out transesterification reaction, steam the methyl alcohol that is generated simultaneously;
Said dibasic alcohol is selected from 1, the mixture that 4-butyleneglycol and one or more other dibasic alcohol are formed, and said other dibasic alcohol is selected from ethylene glycol, 1, ammediol, 1,6-hexylene glycol or glycol ether;
(2) with the product of aliphatic dicarboxylic acid and stablizer adding step (1), carry out esterification, get rid of the water that reaction generates simultaneously, at 220～240 ℃, the copolycondensation of reducing pressure under 90～133Pa obtains multipolymer;
Select oneself in diacid, nonane diacid, sebacic acid, undecandioic acid or 12 diacid one or more of said aliphatic dicarboxylic acid;
Said stablizer is selected from trimethyl phosphite 99 or triphenyl phosphite.
2. method according to claim 1 is characterized in that, the temperature of reaction of step (1) is 150～205 ℃, when the methyl alcohol quantity of distillate be theoretical amount 90～95% the time, transesterification reaction finishes.
3. method according to claim 1 is characterized in that, the mol ratio of dimethyl terephthalate (DMT) and dibasic alcohol is 1: 1.0～1.7.
4. method according to claim 1 is characterized in that said catalyzer is selected from tetraethyl titanate, titanium isopropylate or tetrabutyl titanate, and the molar weight of used catalyzer is 0.01%～0.05% of a dimethyl terephthalate (DMT).
5. method according to claim 1 is characterized in that, 1, and the mol ratio of 4-butyleneglycol and other dibasic alcohol is 1: 0.2～1.0.
6. method according to claim 1 is characterized in that, the temperature of reaction of step (2) is 190～220 ℃, when the quantity of distillate of water be theoretical amount 90～95% the time, the copolycondensation of reducing pressure.
7. method according to claim 1 is characterized in that, the mol ratio of aliphatic dicarboxylic acid and dibasic alcohol is 1: 1.0～1.8;
The mol ratio of dimethyl terephthalate (DMT) and aliphatic dibasic acids is 1: 0.2～1.0; Be preferably 0.6～0.8.
8. method according to claim 1 is characterized in that, stabilizing agent dosage be step (2) product weight 0.02%～0.06%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100337541A CN101245230A (en) | 2008-02-21 | 2008-02-21 | Method for manufacturing linear copolyester hot melt adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100337541A CN101245230A (en) | 2008-02-21 | 2008-02-21 | Method for manufacturing linear copolyester hot melt adhesive |
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| CN101245230A true CN101245230A (en) | 2008-08-20 |
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| CNA2008100337541A Pending CN101245230A (en) | 2008-02-21 | 2008-02-21 | Method for manufacturing linear copolyester hot melt adhesive |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367914B (en) * | 2008-10-10 | 2011-01-19 | 北京服装学院 | Method for preparing low-melting point polyester with interesterification method |
| CN102432854A (en) * | 2011-08-31 | 2012-05-02 | 常州天马集团有限公司 | Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer |
| CN101724373B (en) * | 2009-11-19 | 2012-07-04 | 北京高盟新材料股份有限公司 | Preparation method of hot-melt reaction type adhesive for composite material |
| CN101724370B (en) * | 2009-11-19 | 2012-12-12 | 北京高盟新材料股份有限公司 | Preparation method of binding agent applied to environment-friendly aluminum structure composite material |
| CN103468195A (en) * | 2013-09-26 | 2013-12-25 | 上海天洋热熔胶有限公司 | Preparation method of biodegradable polyester hot melt adhesive |
| CN107513362A (en) * | 2016-08-01 | 2017-12-26 | 华特粘接材料股份有限公司 | The preparation method of transparent polyester PUR |
| CN107541182A (en) * | 2017-08-03 | 2018-01-05 | 苏州艾普娜斯纺织品有限公司 | Transparent copolyester hot-melt adhesive granules |
| CN110078907A (en) * | 2019-04-17 | 2019-08-02 | 金晖兆隆高新科技股份有限公司 | A kind of biology base Biodegradable polyester and its synthetic method |
| CN111423567A (en) * | 2019-01-10 | 2020-07-17 | 圆益Bm科技有限公司 | Polymer compound and method for producing same |
| CN111463368A (en) * | 2019-01-22 | 2020-07-28 | 圆益Bm科技有限公司 | Battery packaging material |
| CN113321795A (en) * | 2021-06-15 | 2021-08-31 | 桂林理工大学 | PBT/artificial granite waste residue composite material and preparation method thereof |
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2008
- 2008-02-21 CN CNA2008100337541A patent/CN101245230A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367914B (en) * | 2008-10-10 | 2011-01-19 | 北京服装学院 | Method for preparing low-melting point polyester with interesterification method |
| CN101724373B (en) * | 2009-11-19 | 2012-07-04 | 北京高盟新材料股份有限公司 | Preparation method of hot-melt reaction type adhesive for composite material |
| CN101724370B (en) * | 2009-11-19 | 2012-12-12 | 北京高盟新材料股份有限公司 | Preparation method of binding agent applied to environment-friendly aluminum structure composite material |
| CN102432854A (en) * | 2011-08-31 | 2012-05-02 | 常州天马集团有限公司 | Polyester plasticizer for leading glass fiber to form felt and preparation method of polyester plasticizer |
| CN103468195A (en) * | 2013-09-26 | 2013-12-25 | 上海天洋热熔胶有限公司 | Preparation method of biodegradable polyester hot melt adhesive |
| CN107513362A (en) * | 2016-08-01 | 2017-12-26 | 华特粘接材料股份有限公司 | The preparation method of transparent polyester PUR |
| CN107541182A (en) * | 2017-08-03 | 2018-01-05 | 苏州艾普娜斯纺织品有限公司 | Transparent copolyester hot-melt adhesive granules |
| CN111423567A (en) * | 2019-01-10 | 2020-07-17 | 圆益Bm科技有限公司 | Polymer compound and method for producing same |
| CN111463368A (en) * | 2019-01-22 | 2020-07-28 | 圆益Bm科技有限公司 | Battery packaging material |
| CN110078907A (en) * | 2019-04-17 | 2019-08-02 | 金晖兆隆高新科技股份有限公司 | A kind of biology base Biodegradable polyester and its synthetic method |
| CN113321795A (en) * | 2021-06-15 | 2021-08-31 | 桂林理工大学 | PBT/artificial granite waste residue composite material and preparation method thereof |
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Open date: 20080820 |