CN101126005A - Polyester thermosol and preparation method thereof - Google Patents
Polyester thermosol and preparation method thereof Download PDFInfo
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- CN101126005A CN101126005A CNA2007100432363A CN200710043236A CN101126005A CN 101126005 A CN101126005 A CN 101126005A CN A2007100432363 A CNA2007100432363 A CN A2007100432363A CN 200710043236 A CN200710043236 A CN 200710043236A CN 101126005 A CN101126005 A CN 101126005A
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Abstract
The invention provides a polyester hot melt adhesive and a preparation method thereof, comprising the steps that: (1) in the presence of a catalyst, a transesterification is carried out between a dimethyl terephthalate and a diol; (2) a isophthalic acid, a aliphatic dicarboxylic acid and a stabilizer are mixed with the yield products of the step (1), a decompression and a co-condensation process are carried out so as to obtain a copolymer; (3) the mixture of a sorbic acid metal salt and the copolymer of ethylene KEYI acrylic acid are added in the yield products of step (2), then the copolymer is modified so as to obtain the polyester hot melt adhesive. The invention adopts the sorbic acid metal salt and the copolymer of ethylene acrylic acid to modify the colopolymer. The polyester hot melt adhesive obtained therefrom has the advantages of strong bond performance, positive effects of water cleaning and dry cleaning resistances, short opening time and fast solidification. The polyester hot melt adhesive is especially suitable for a production assembly line which calls for rapid bonding.
Description
Technical field
The present invention relates to a kind of polyester hot-melt adhesive and manufacture method thereof, relate in particular to a kind of manufacture method based on organic polymer synthetic polyester hot-melt adhesive.
Background technology
Polyester hot-melt adhesive has purposes more widely, is particularly useful for the bonding processing of lining cloth.
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.1760304 of Chinese patent CN pass through to introduce 3,5-orcin and 3, and 5-resorcylic acid modification by copolymerization obtains a kind of low-melting polyester hot-melt adhesive.
But, from prior art, the lower polyester hot-melt adhesive of the fusing point of developing, its curing speed is also slower, and this will cause the sticking back of the body phenomenon in the lining cloth course of processing.Therefore, developing lower, the fast polyester hot-melt adhesive of curing speed simultaneously of a kind of fusing point, is that institute of relevant branch of industry is very expected.
Summary of the invention
The purpose of this invention is to provide a kind of polyester hot-melt adhesive and preparation method thereof,, satisfy the needs in relevant field to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) with dimethyl terephthalate (DMT) and dibasic alcohol under catalyst action, carry out transesterification reaction under nitrogen protection, temperature of reaction is 140～200 ℃, steams the methyl alcohol that is generated simultaneously, when the methyl alcohol quantity of distillate be theoretical amount 88～95% the time, transesterification reaction finishes;
The mol ratio of said dimethyl terephthalate (DMT) and dibasic alcohol is 1:1.1～1.4;
Said catalyzer is selected from titanate ester, preferred tetraethyl titanate, titanium isopropylate, tetrabutyl titanate, and used catalyzer molar weight is 0.01%～0.1% of a dimethyl terephthalate (DMT);
Said dibasic alcohol is 1, the mixture that 4-butyleneglycol and one or more other dibasic alcohol are formed, said other dibasic alcohol is selected from ethylene glycol, 1, ammediol,, hexylene glycol or glycol ether.
(2) m-phthalic acid, aliphatic dicarboxylic acid and stablizer are added the product of step (1), carry out esterification, temperature is 180～210 ℃, get rid of the water that reaction generates simultaneously, when the quantity of distillate of water be theoretical amount 88～95% the time, at 220～240 ℃, 80～133Pa decompression copolycondensation down, time is 0.5～4.5 hour, obtains multipolymer;
The total acid in the said esterification and the mol ratio of dibasic alcohol are 1: 1.0～1.2;
The mol ratio of dimethyl terephthalate (DMT) and m-phthalic acid is 1: 0.6～1.0;
M-phthalic acid and aliphatic dicarboxylic acid's mol ratio is: 1: 0.15～0.3;
Said stablizer is selected from phosphoric acid ester, preferably phosphoric acid trimethyl, triphenyl phosphite, stabilizing agent dosage be step (2) product weight 0.02%～0.06%;
Said aliphatic dibasic acids select oneself diacid, suberic acid, nonane diacid or sebacic acid;
(3) under nitrogen protection, the deactivation system vacuum state is under 220～240 ℃ and normal pressure; the product that the mixture of the metal-salt of Sorbic Acid and ethylene/acrylic acid copolymer is added step (2); constant temperature stirred 0.5 hour, and multipolymer is carried out modification, got polyester hot-melt adhesive.
The metal-salt of said Sorbic Acid is selected from potassium sorbate, sodium sorbate or calcium sorbate etc., and its weight consumption is 0.01%～0.1% of a dimethyl terephthalate (DMT);
The molecular weight of said ethylene/acrylic acid copolymer is 3000～5000, and weight consumption is 0.01%～0.1% of a dimethyl terephthalate (DMT).
Compared with prior art, the present invention has following positively effect:
1. the present invention adopts the metal-salt of Sorbic Acid and a kind of ethylene/acrylic acid copolymer that above-mentioned multipolymer is carried out modification, and it is big that the gained polyester hot-melt adhesive has bonding strength, the positively effect of ability washing and dry-cleaning.
2. the polyester hot-melt adhesive of the used technology manufacturing of the present invention has the advantages that the open hour are short, curing speed is fast, and the spy is applicable to need finish fast on the bonding generation streamline and uses.
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), glycol ether (50g), catalyzer metatitanic acid four butyl esters (0.50g), heating, material begins fusing when interior temperature reaches 145 ℃, begins then to stir; When being warmed up to 148 ℃ of left and right sides, begin to distillate methyl alcohol, temperature reaches 180～195 ℃ 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 m-phthalic acid (290g), sebacic acid (7g), 1,4-butyleneglycol (200g), ethylene glycol (30g), and adding stablizer triphenyl phosphite (0.25g), stir to heat up then, when interior temperature rise to the 180 ℃ 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 89% after, continue to heat up, when interior temperature reaches 230 ℃, 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 133Pa, in 2.0 hours reaction times, polycondensation finishes.Under nitrogen protection, the deactivation system vacuum state is under 230 ℃ and normal pressure; the mixture of potassium sorbate (0.5g) and ethylene/acrylic acid copolymer (0.6g, molecular weight 3200) is added the product of step (2), and constant temperature stirred 0.5 hour; multipolymer is carried out modification, get polyester hot-melt adhesive.In the nitrogen protection bottom discharge, be cut into particle.
Detect according to standard GB/T4608-84, GB/T3682-2000 and ministerial standard HG/T3716 respectively, the fusing point of this product is 115～120 ℃, melts to refer to be that 18.5g/10min, open hour are 2.8min.
Embodiment 2
In having the polymerization reaction kettle of water distilling apparatus, 2.0L adds dimethyl terephthalate (DMT) (333g), and 1,4-butyleneglycol (210g), glycol ether (40g), catalyzer metatitanic acid tetra-ethyl ester (0.45g), heating, material begins fusing when interior temperature reaches 145 ℃, begins then to stir; When being warmed up to 148 ℃ of left and right sides, begin to distillate methyl alcohol, temperature reaches 180～195 ℃ in continuing to be warming up to, and treats that distilled methyl alcohol reaches 91% o'clock of theoretical amount, and transesterification reaction finishes.
In above-mentioned reactant, add m-phthalic acid (290g), hexanodioic acid (8.0g), 1,4-butyleneglycol (190g), ethylene glycol (45g), and adding stablizer triphenyl phosphite (0.25g), stir to heat up then, when interior temperature rise to the 180 ℃ left and right sides, begin to have water to distillate, continue to be warming up to 204 ℃, 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 reduced or be slack-off, the high vacuum reaction was carried out in decompression, and system pressure remains on below the 120Pa, in 2.0 hours reaction times, polycondensation finishes.Under nitrogen protection, the deactivation system vacuum state is under 230 ℃ and normal pressure; the mixture of sodium sorbate (0.7g) and ethylene/acrylic acid copolymer (0.8g, molecular weight 3900) is added the product of step (2), and constant temperature stirred 0.5 hour; multipolymer is carried out modification, get polyester hot-melt adhesive.In the nitrogen protection bottom discharge, be cut into particle.
Detect according to standard GB/T4608-84, GB/T3682-2000 and ministerial standard HG/T3716 respectively, the fusing point of this product is 105～115 ℃, melts to refer to be that 22.8g/10min, open hour are 2.6min.
Embodiment 3
In having the polymerization reaction kettle of water distilling apparatus, 2.0L adds dimethyl terephthalate (DMT) (333g), and 1,4-butyleneglycol (200g), 1, ammediol (48g), catalyzer metatitanic acid orthocarbonate (0.50g), heating, material begins fusing when interior temperature reaches 145 ℃, begins then to stir; When being warmed up to 148 ℃ of left and right sides, begin to distillate methyl alcohol, temperature reaches 180～195 ℃ 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 m-phthalic acid (290g), nonane diacid (10g), 1,4-butyleneglycol (200g), ethylene glycol (30g), and adding stablizer triphenyl phosphite (0.25g), stir to heat up then, 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 93% after, continue to heat up, when interior temperature reaches 230 ℃, 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 100Pa, in 2.0 hours reaction times, polycondensation finishes.Under nitrogen protection, the deactivation system vacuum state is under 240 ℃ and normal pressure; the mixture of calcium sorbate (0.7g) and ethylene/acrylic acid copolymer (0.7g, molecular weight 4200) is added the product of step (2), and constant temperature stirred 0.5 hour; multipolymer is carried out modification, get polyester hot-melt adhesive.In the nitrogen protection bottom discharge, be cut into particle.
Detect according to standard GB/T4608-84, GB/T3682-2000 and ministerial standard HG/T3716 respectively, the fusing point of this product is 112～118 ℃, melts to refer to be that 21.5g/10min, open hour are 2.8min.
Claims (9)
1. a preparation method of polyester hot melt adhesive is characterized in that, comprises the steps:
(1) with dimethyl terephthalate (DMT) and dibasic alcohol under catalyst action, under nitrogen protection, carry out transesterification reaction, temperature of reaction is 140～200 ℃, the methyl alcohol that this reaction generated is steamed, react to the methyl alcohol quantity of distillate be 88～95% of theoretical amount; Said catalyzer is selected from titanate ester;
(2) m-phthalic acid, aliphatic dicarboxylic acid and stablizer are added the product of step (1), carry out esterification, temperature is 180～210 ℃, the water that this reaction generated is steamed, react to the quantity of distillate of water be theoretical amount 88～95% after, at 220～240 ℃, down decompression copolycondensation of 80～133Pa, time is 0.5～4.5 hour, obtains multipolymer; Said stablizer is selected from phosphoric acid ester;
(3) under nitrogen protection, the deactivation system vacuum state is under 220～240 ℃ and normal pressure; the product that the mixture of the metal-salt of Sorbic Acid and ethylene/acrylic acid copolymer is added step (2); constant temperature stirred 0.5 hour, and multipolymer is carried out modification, got polyester hot-melt adhesive.
2. method according to claim 1 is characterized in that catalyzer is selected from tetraethyl titanate, titanium isopropylate, tetrabutyl titanate, and used catalyzer molar weight is 0.01%～0.1% of a dimethyl terephthalate (DMT).
3. method according to claim 1, it is characterized in that said dibasic alcohol is selected from 1, the mixture that 4-butyleneglycol and one or more other dibasic alcohol are formed, said other dibasic alcohol is selected from ethylene glycol, 1, ammediol,, hexylene glycol or glycol ether.
4. method according to claim 1 is characterized in that, the total acid in the said esterification and the mol ratio of dibasic alcohol are 1: 1.0～1.2;
The mol ratio of dimethyl terephthalate (DMT) and m-phthalic acid is 1: 0.6～1.0;
M-phthalic acid and aliphatic dicarboxylic acid's mol ratio is: 1: 0.15～0.3.
5. method according to claim 1 is characterized in that, said aliphatic dibasic acids select oneself diacid, suberic acid, nonane diacid or sebacic acid.
6. method according to claim 1 is characterized in that said stablizer is selected from trimethyl phosphite 99, triphenyl phosphite, stabilizing agent dosage be step (2) product weight 0.02%～0.06%.
7. method according to claim 1 is characterized in that, in the step (1), the mol ratio of dimethyl terephthalate (DMT) and dibasic alcohol is 1: 1.1～1.4.
8. according to each described method of claim 1～7, it is characterized in that the metal-salt of said Sorbic Acid is selected from potassium sorbate, sodium sorbate or calcium sorbate etc., its weight consumption is 0.01%～0.1% of a dimethyl terephthalate (DMT); The molecular weight of said ethylene/acrylic acid copolymer is 3000～5000, and weight consumption is 0.01%～0.1% of a dimethyl terephthalate (DMT).
9. adopt the polyester hot-melt adhesive of each described method preparation of claim 1～9.
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| CNB2007100432363A CN100439466C (en) | 2007-06-29 | 2007-06-29 | Polyester thermosol and preparation method thereof |
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| CNB2007100432363A CN100439466C (en) | 2007-06-29 | 2007-06-29 | Polyester thermosol and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519574B (en) * | 2009-04-07 | 2012-02-08 | 北京高盟新材料股份有限公司 | Preparation method of thermosetting type composite adhesive |
| CN101701141B (en) * | 2009-08-31 | 2012-09-05 | 北京高盟新材料股份有限公司 | Preparation method of monocomponent moisturecured bonding agent for reflecting material |
| CN103184027A (en) * | 2011-12-28 | 2013-07-03 | 上海轻工业研究所有限公司 | Low-viscosity polyester hot melt adhesive and preparation method thereof |
| CN104650332A (en) * | 2014-12-09 | 2015-05-27 | 福建天大化工有限公司 | Preparation method of resin intermediate--phthalic acid diethylene glycol polyester |
| CN105433450A (en) * | 2016-01-26 | 2016-03-30 | 广东宏杰内衣实业有限公司 | Micro-vibration massage bra and making method thereof |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19831366A1 (en) * | 1998-07-13 | 2000-01-27 | Inventa Ag | Deep-melting copolyester or copolyetherester hotmelt adhesives |
| CN1138841C (en) * | 2000-08-29 | 2004-02-18 | 上海理日科技发展有限公司 | Process for preparing polyester thermosol with high smelting point |
| CN1308410C (en) * | 2005-11-14 | 2007-04-04 | 上海轻工业研究所有限公司 | Composition of polyester hot-melt adhesive in low melting viscosity |
-
2007
- 2007-06-29 CN CNB2007100432363A patent/CN100439466C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519574B (en) * | 2009-04-07 | 2012-02-08 | 北京高盟新材料股份有限公司 | Preparation method of thermosetting type composite adhesive |
| CN101701141B (en) * | 2009-08-31 | 2012-09-05 | 北京高盟新材料股份有限公司 | Preparation method of monocomponent moisturecured bonding agent for reflecting material |
| CN103184027A (en) * | 2011-12-28 | 2013-07-03 | 上海轻工业研究所有限公司 | Low-viscosity polyester hot melt adhesive and preparation method thereof |
| CN103184027B (en) * | 2011-12-28 | 2015-05-13 | 上海轻工业研究所有限公司 | Low-viscosity polyester hot melt adhesive and preparation method thereof |
| CN104650332A (en) * | 2014-12-09 | 2015-05-27 | 福建天大化工有限公司 | Preparation method of resin intermediate--phthalic acid diethylene glycol polyester |
| CN104650332B (en) * | 2014-12-09 | 2017-01-11 | 福建天大化工有限公司 | Preparation method of resin intermediate--phthalic acid diethylene glycol polyester |
| CN105433450A (en) * | 2016-01-26 | 2016-03-30 | 广东宏杰内衣实业有限公司 | Micro-vibration massage bra and making method thereof |
| 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 |
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| CN100439466C (en) | 2008-12-03 |
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Effective date of registration: 20220329 Address after: 226000 phase I of Lingang Industrial Zone, Weisan Road, Yangkou Port Economic Development Zone, Rudong County, Nantong City, Jiangsu Province Patentee after: Nantong Tianyang photovoltaic material technology Co.,Ltd. Address before: 201802 Shanghai city Jiading District Nanxiang Hui Ping Road No. 505 Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. |
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